In the past decade there has been a growing interest in one-dimensional (1D) nanostructures, such as nanowires, nanotubes and nanorods, owing to their size-dependent optical and electronic properties and their potential application as building blocks, interconnects and functional components for assembling nanodevices. One of the ways to obtain such architectures is a template-directed synthesis which is practically a straightforward route to 1D nanostructures. In this approach, the template simply serves as a scaffold, within (or around) which a different material is generated in situ and shaped into a nanostructure with its morphology complementary to that of the template. It is generally accepted that template-directed synthesis provides a simple, high-throughput, and cost-effective procedure that also allows the complex topology present on the surface of a template to be duplicated in a single step. In the current work, utilization of the molecular bottle brushes as templates is proposed for the fabrication of conductive nanorods. Their non-spherical macromolecular geometries and lengths up to a few hundred nanometers allow the application of these structures in nanowire synthesis. The variety of molecular bottle brush architectures and their composition enables the adjustment of appropriate conditions for the preparation of conductive materials. Moreover, the ability of the brushes to assemble on a surface under certain conditions provides their usage as building blocks for the preparation of complex conductive networks. Here, the preparation, characterization, and applications of molecular bottle brushes are discussed. Two main goals were pursued. First, to deepen the knowledge in the synthesis of molecular bottle brushes, and to investigate their behavior on the surface. Second, to explore the application of the brushes as templates or building blocks for the formation of conductive nanowires. For the purpose, new ways of molecular brush synthesis by using the “grafting to” approach had to be developed. It was found that the reaction of nucleophilic addition based on pentofluorophenol chemistry and a coupling “click chemistry” reaction can be used to fabricate molecular brushes. Both methods showed efficient results and demonstrated high reactivity of the backbone with the end groups of the side chains. The “click chemistry” approach, however, demonstrated better results considering higher thicknesses of the brushes and, therefore, higher grafting density of the side chains. The “grafting to” together with the “grafting from” methods are very powerful synthetic tools, which can be used in the fabrication of any desired molecular bottle brush architectures. Additionally, complexation of oppositely charged bottle polymer brushes at a single-molecule level using AFM and CryoTEM was experimentally investigated. It was found that polyelectrolyte complexes have “scrambled-egg” morphology, where oppositely charged polymer chains are not oriented parallel to each other but cross each other. Furthermore, molecular bottle brushes were used as templates for the preparation of conductive nanowires. Three approaches for their fabrication were tested. It was found that brushes could easily be covered with various conductive materials, for example conductive polymers or metals. It was showed that for very small, tiny objects as molecular bottle brushes, one can use FIB in order to build up electrodes at its ends. The electrodes could be sputtered with an accuracy of 500 nm and further be used in the determination of the conductivity. The molecular bottle brushes covered with palladium showed the resistance of 50 MΩ, which, regarding the size of the brush, corresponds to a conductivity of one single molecule being ~1 S*cm-1. The obtained conductivity data were in good correlation with the data found in literature. We believe that the molecular bottle brushes have high potential applicability for the building of complex conductive networks. Future refinement of the synthetic methods, combined with improvements in structuring and positioning of objects at the nanoscale, could lead to their implementation in the construction of high-performance electronic devices.

Diese Dissertation beschreibt die Synthese und Charakterisierung neuartiger Hyperstern-Polymere (HSP) und deren Funktion als Reaktivbinder in Epoxy- bzw. PUR-Harzen. Hyperstern-Polymere sind Hybride aus hochverzweigten (hvz) und linearen Polymeren. Sie können über ihre reaktiven OH-Gruppen als multifunktionelle hochverzweigte Quervernetzer kovalent in ein kationisch härtendes Epoxyharz einbinden und thermische sowie thermomechanische Eigenschaften verbessern.:Theoretischer Teil Einleitung und Aufgabenstellung Grundlagen 1 Polymeraufbau 1.1. Radikalische Polymerisationen 1.1.1. Kontrolliert radikalische Polymerisation 1.1.2. NMRP 1.1.3. ATRP 1.1.4. RAFT 1.2. Anionische Polymerisation 1.3. Kationische Polymerisation 1.3.1. CROP von Oxazolinen 1.4. Koordinative Polymerisationen 2 Verzweigte Polymerarchitekturen 2.1. Dendritische Polymere 2.1.1. Dendrimere 2.1.2. Hochverzweigte Polymere 2.1.2.1 SCVP 2.1.3. Dendrigrafts 2.1.4. Dendronisierte Polymere 2.2. Spezielle Polymerarchitekturen 2.2.1. Hyperstern-Polymere (HSP) 3 Lacke 3.1. Lösungsmittelhaltige Lacke 3.1.1. Chemisch härtende Lacke 3.1.2. Physikalisch trocknende Lacke 3.2. Wässrige Lacke 3.3. Lösungsmittelfreie Lacke 3.3.1. Strahlenhärtende Lacke 3.3.2. Pulverlacke 3.4. Aliphatische Epoxylacke 3.4.1. UV-Härtung 3.4.2. Thermische Härtung 3.4.3. Thermische Härtung klassischer 2K-Polyepoxid-Lacke 3.5. 2K-PUR-Lacke 3.6. Aktuelle Herausforderungen 3.7. Wissenschaftliche Konzepte zur Schlagzähmodifizierung von Lacken Diskussion und Ergebnisse 4 Synthese hochverzweigter Makroinitiatoren 4.1. Polyester-Makroinitiatoren PE-MI1 und PE-MI2 4.1.1. Polyester-Kern (PE-OH) 4.1.2. Makroinitiatoren für die Oxazolinpolymerisation (PE-MI1) 4.1.3. Makroinitiatoren für die ATRP von Methacrylaten (PE-MI2) 4.2. Poly(vinylbenzylchlorid)-Makroinitiator (PVBC) 5 Hypersterne mit POxa-Armen 5.1. Lineare Polyoxazolin-Modellverbindungen (POxa) 5.1.1. Test der Initiatorfunktionen 5.1.2. Einfluss der Mikrowelle 5.1.3. Terminierung (Capping) 5.1.4. Polymerisation OH-tragender Oxazoline 5.1.5. Adamantan-funktionalisierte Polyoxazoline 5.2. Hypersterne aus Polyester-Kern sowie Polyoxazolin-Armen: PE-g-POxa 5.2.1. Einführung von OH-Gruppen über die Terminierung 5.2.2. Einführung von OH-Gruppen über die Wiederholeinheiten 5.3. Hypersterne aus Polyvinylbenzylchlorid-Kern sowie Polyoxazolin-Armen: PVBC-g-POxa 5.3.1. Modellinitiatoren 5.3.2. Einführung von OH-Gruppen über die Wiederholeinheiten 5.4. Ausblick: Arm first-Strategie 6 Hypersterne mit Polymethacrylat-Armen 6.1. Hypersterne aus Polyvinylbenzylchlorid-Kern sowie Polymethacrylat-Armen: PVBC-g-PHEMA 6.2. Hypersterne aus Polyester-Kern sowie Polymethacrylat-Armen: PE-g-(PMMA-b-HEMA) 7 Hypersterne als Quervernetzer-Additive in Lacken 7.1. PVBC-g-POxa in Epoxyharz 7.1.1. Thermische Härtung 7.2. PE-g-P(MMA-b-HEMA) in Epoxyharz 7.2.1. UV-Härtung 7.2.2. Thermische Härtung 7.3. PE-g-P(MMA-b-HEMA) in 2K-PUR-Harz Zusammenfassung – Ausblick Experimenteller Teil 8 Geräte, Methoden und Chemikalien 9 Synthesen 9.1. Monomere, Capper, Niedermolekulare Substanzen 9.2. Lineare Polyoxazoline 9.2.1. Niedermolekulare CROP-Initiatoren 9.2.2. Lineares Poly(2-methyloxazolin) (PMeOxa) 9.2.3. Adamantan-funktionalisierte Poly(2-methyloxazoline) 9.2.4. Lineare Poly(2-ethyloxazoline) 9.2.5. NMR-Modellverbindungen für PVBC-Kern 9.3. Hochverzweigte Polymere und Makroinitiatoren 9.4. Hyperstern-Polymere mit POxa-Armen 9.5. Hyperstern-Polymere mit PAlkMA-Armen 9.6. Lackproben Abkürzungsverzeichnis Literaturverzeichnis Publikationsliste

Poly(dimethylsiloxan) (PDMS) ist ein wichtiges Polymer, das zunehmend in der Mikroelektronik aufgrund seiner hervorragenden Elastizität und thermischen Stabilität Verwendung findet. Ein limitierender Faktor für den Einsatz von PDMS ist aufgrund des Fehlens von reaktiven Gruppen und der niedrigen freien Oberflächenenergie seine geringe Adhäsion zu anderen Materialien. Zur Erhöhung der Adhäsion ist deshalb die Einführung von polaren, funktionellen Gruppen notwendig. Hier lag die Motivation der vorliegenden Arbeit, die sich eine gezielte Funktionalisierung von PDMS-Oberflächen als Aufgabe gesetzt hatte. Im ersten Teil der Arbeit wurde eine Verbesserung der Adhäsion zu einem fotostrukturierbaren Epoxidharz mittels der Sauerstoff- und Ammoniakplasmabehandlung angestrebt. In beiden Fällen führte die Plasmabehandlung zu der Einführung von unterschiedlichsten funktionellen Gruppen auf die Oberfläche und zu einer Verbesserung des Benetzungsverhaltens gegenüber Wasser. Zudem wurden Haftfestigkeiten erzielt, die um ein Vielfaches höher waren als jene zwischen Epoxidharz und einer unbehandelten PDMS-Oberfläche. Jedoch waren die hydrophilen Eigenschaften nach der Plasmabehandlung während der Lagerung an Luft zeitlich begrenzt, die PDMS-Oberfläche kehrt innerhalb kurzer Zeit in den einst hydrophoben Ausgangszustand zurück. Der Alterungsvorgang wird als „Hydrophobic Recovery“ bezeichnet und ist bei PDMS-Oberflächen, die höheren Plasmaleistungen und Behandlungszeiten ausgesetzt wurden, besonders auffällig. Die Vermeidung dieser Problematik war der Ausgangspunkt für den zweiten Teil der Arbeit. Auf der Grundlage der über die Plasmabehandlungen erzeugten funktionellen Gruppen wurden neue Konzepte für eine kovalente Anbindung von verschiedenen funktionellen Homo- und Copolymeren über die „Grafting to“-Technik entwickelt. Neben der Erhöhung der Adhäsion zu dem Epoxidharz war es möglich, das Benetzungsverhalten gegenüber Wasser durch die Unterbindung der „Hydrophobic Recovery“ zu stabilisieren. Des Weiteren gelang es, durch die Wahl der funktionellen Polymere, die PDMS-Oberfläche gezielt mit gewünschten Eigenschaften auszustatten. Somit ist der Einsatz der polymermodifizierten Oberflächen, außer in der Mikroelektronik, auch auf andere Anwendungen, wie der Biomedizin, der Mikrofluidik oder der Softlithografie übertragbar, in denen eine beständige, definierte Oberflächenfunktionalisierung ein wichtiges Kriterium darstellt.

Die vorliegende Arbeit liefert einen Beitrag zum Verständnis der komplexen Struktur-/Eigenschaftsbeziehungen dünner Schichten hochverzweigter Polyester. Für die umfassende Charakterisierung wurde eine Vielzahl analytischer Methoden kombiniert. Des Weiteren wurde das Anwendungspotential dieser Schichten hinsichtlich möglicher Sensoranwendung anhand der Adsorption von Modellproteinen gewichtet. Dazu war es notwendig verschieden Methoden zur Stabilisierung dieser Schichten zu entwickeln.

Thesis (MSc) -- Stellenbosch University, 1975. / No abstract available

Molecular transport through hollow cores of crystalline carbon nanotubes (CNTs) are of considerable interest from the fundamental and application point of view. This dissertation focuses on understanding molecular transport through a membrane platform consisting of open ended CNTs with ~ 7 nm core diameter and ~ 1010 CNTs/cm2 encapsulated in an inert polymer matrix. While ionic diffusion through the membrane is close to bulk diffusion expectations, gases and liquids were respectively observed to be transported ~ 10 times faster than Knudsen diffusion and ~ 10000-100000 times faster than hydrodynamic flow predictions. This phenomenon has been attributed to the non-interactive and frictionless graphitic interface. Functionalization of the CNT tips was observed to change selectivity and flux through the CNT membranes with analogy to gate-keeper functionality in biological membranes. An electro-chemical diazonium grafting chemistry was utilized for enhancing the functional density on the CNT membranes. A strategy to confine the reactions at the CNT tips by a fast flowing liquid column was also designed. Characterization using electrochemical impedance spectroscopy and dye assay indicated ~ 5-6 times increase in functional density. Electrochemical impedance spectroscopy experiments on CNT membrane/electrode functionalized with charged macro-molecules showed voltage-controlled conformational change. Similar chemistry has been applied for realizing voltage-gated transport channels with potential application in trans-dermal drug delivery. Electrically-facilitated transport ( a geometry in which an electric field gradient acts across the membrane) through the CNT and functionalized CNT membranes was observed to be electrosmotically controlled. Finally, a simulation framework based on continuum electrostatics and finite elements has been developed to further the understanding of transport through the CNT membranes.

Surface-initiated photo-iniferter mediated controlled polymerisation was used as a technique for the development of advanced and smart materials. Molecularly imprinted polymer (MIP) shell nanoparticles (NPs) were synthesised in this way from PAMAM dendrimers, used as a graftable core, in 2 min irradiation time. Surprisingly the so-synthetised NPs were around 200 nm and had a cubic shape. Cont/d.

Master of Science / Department of Horticulture, Forestry, and Recreation Resources / Cary L. Rivard / Grafting with inter-specific hybrid rootstock is effective for tomato (Solanum lycopersicum) growers looking to reduce soilborne disease organically and increase fruit yield in the Southeastern US. However, production with grafted tomatoes has not been tested in the Great Plains region of the US. Small-acreage growers would like to produce grafted plants themselves, but many have difficulty with propagation due to water stress in the scion post-grafting and/or high temperatures within healing chambers. Growers may be able to reduce water stress post-grafting by removing the upper portion of the shoot to reduce leaf surface area, but no data exist on the potential effects of this practice on mature plant yield. Five high tunnel and one open-field study were conducted in 2011 and 2012 to investigate yield effects related to the use of two rootstocks and shoot removal during the grafting procedure. Grafting significantly increased fruit yield in five of the six trials (P<0.05). The average yield increases by Maxifort and ‘Trooper Lite’ rootstocks were 53% and 51%, respectively, across all trials. In some trials shoot removal during the grafting process reduced yield and could depend upon rootstock vigor. Another series of experiments were performed testing the efficacy of shoot removal for graft survival during the healing period prior to field planting. Five healing chambers designs were evaluated, and no significant effects of treatment design were observed upon grafted seedling survival. Plants grafted with no chamber had success rates of 81% to 91%. Additionally, three grafting leaf removal techniques were studied, and a partial leaf removal method had significantly higher success rates as compared to fully foliated and defoliated plants (P<0.05). Partial leaf removal may be recommended as a way to reduce water stress in the plant, and could potentially be a way to simplify the grafting process for small-scale producers.

Dentre os métodos utilizados na propagação vegetativa de espécies florestais, a enxertia por borbulhia é a mais empregada para a seringueira (Hevea brasiliensis). Nesse sistema de produção de mudas, os porta-enxertos são formados diretamente no solo ou em sacos de polietileno preenchidos com solo. Embora essa seja uma prática comum nos viveiros, mudanças nos parâmetros legais foram propostas a fim de alterar o sistema de produção de mudas, principalmente no que diz respeito ao cultivo dos porta-enxertos. Para atender essas alterações, objetivou-se desenvolver um protocolo de produção de mudas de seringueira em bancadas suspensas. Para isso, foram conduzidos dois experimentos (descritos no cap. II e III) em Piracicaba - SP. No capítulo II, propõe-se a produção de hastes verdes em minijardim clonal hidropônico com leito de areia. Doses crescentes de nutrientes via fertirrigação foram testadas. Avaliou-se a produtividade do minijardim em função da fertirrigação e o aproveitamento das hastes verdes para a enxertia. Os resultados obtidos, mostraram que a fertirrigação afetou a produção de hastes verdes de seringueira em condições de minijardim clonal, sendo 1,5 mS cm-1 a condutividade elétrica ideal da solução nutritiva para produção de hastes verdes nesse sistema. Mesmo sob sistema hidropônico em casa de vegetação, forte sazonalidade da produção foi observada. As melhores estações do ano para coletar hastes verdes aptas às enxertias por borbulhia e garfagem foram à primavera e o verão. Nesse período recomenda-se elevar a condutividade elétrica da solução para 2,0 mS cm-1. Para o experimento descrito no capítulo III, porta-enxertos foram produzidos em viveiro suspenso, utilizando substrato comercial. Diferentes métodos de enxertia foram testados (borbulhia, garfagem em fenda cheia e fenda lateral) em porta-enxerto com diferentes diâmetros. Os enxertos utilizados foram obtidos no experimento do cap. II. Obteve-se sucesso com a enxertia por borbulhia e a enxertia por garfagem em fenda cheia, sendo possível verificar redução no tempo de produção de mudas de seringueira em condições de viveiro suspenso. No entanto, é necessário ajustes para obter maior sobrevivência das enxertias sob essas condições. / Among methods used for the vegetative propagation of forest species, budding is the most used for rubber tree (Hevea brasiliensis). In this system the rootstocks are produced directly on the soil or in polyethylene bags using soil as substrate. Although this is a common practice in the commercial nurseries, changes in the law were proposed for the planting material production system, particularly in the production of rootstocks. To meet these changes, this work aimed to develop a protocol for the production of rubber tree in suspended benches. There conducted two trials (chapter II and chapter III) in suspended bed in Piracicaba - SP. In chapter II was proposed the production of green scions in hydroponic clonal mini garden in function of fertigation. The mini garden yield was accessed by green scions productions and fertigation. It was found that the fertigation affected the production of green scion of rubber tree under clonal mini garden conditions. The electric conductivity of 1.5 mS cm-1 was the best solution for this system. Even in the hydroponic clonal mini garden in a greenhouse, a strong seasonality of growth was found. The best season to produce green scions in this system was summer and spring. In these seasons it is recommend using the EC of solution of 2.0 mS cm-1. In the experiment described in the chapter III, the rootstocks were produced in suspended benches, using a commercial substrate. Different methods of grafting were tested (budding, grafting in full and lateral cleft) in rootstocks of different diameters. The scions used were obtained in the experiment of chapter II. Success was obtained with the budding and grafting in full cleft, being possible to reduce the period for rubber tree production under suspended benches conditions. Adjustments are needed to get increased grafting survival under these conditions.

OBJETIVO: Determinar a efetividade de manobras padronizadas de drenagem linfática manual (DLM) na redução do edema facial, na distância interincisal máxima ativa e no quadro álgico de pacientes submetidos à cirurgia de Enxerto Ósseo Alveolar (EOA). METODOLOGIA: Esta pesquisa analisou 51 indivíduos com fissura labiopalatina reparada, entre 10 e 15 anos de idade, submetidos ao EOA no Hospital de Reabilitação de Anomalias Craniofaciais-USP, divididos em 2 grupos, grupo tratamento (n=29, 12 homens e 17 mulheres) e grupo rotina (n= 22, 15 homens e 7 mulheres). No grupo tratamento foram aplicadas manobras de DLM padronizadas diferentemente daqueles do grupo rotina. Foram realizadas nos dois grupos avaliações do edema facial por meio das medidas da linha 1 (distância da base da asa nasal ao tragus) e linha 2 (distância da base da asa nasal à implantação inferior do pavilhão auricular), na hemiface operada nos períodos pré-operatório (Pré), segundo (2ºPO) e quarto pós-operatório (4ºPO). Também foram realizadas as medidas da distância interincisal máxima ativa nos mesmos períodos. A Escala Analógica da Dor (EAD) foi aplicada no 1º, 2º, 3º e 4º períodos pós-operatórios. Adicionalmente, no grupo tratamento, após a terapia de DLM, foram realizadas perguntas sobre dor, relaxamento e sono. RESULTADOS: Houve redução do edema facial no grupo tratamento do 2ºPO para o 4ºPO o que não ocorreu no grupo rotina. As medidas da distância interincisal apresentaram aumento entre o 2ºPO e 4ºPO nos dois grupos estudados. Na avaliação da EAD, o grupo tratamento mostrou ausência de dor no 3ºPO enquanto o grupo rotina somente no 4ºPO. No grupo tratamento, a totalidade dos indivíduos relataram que a dor diminuiu, e que se sentiram mais relaxados após a DLM, nos 3 períodos avaliados. Relataram também em muitos casos que a DLM teve efeito facilitador na indução ao sono durante a DLM. CONCLUSÕES: As manobras padronizadas de DLM aplicadas da maneira proposta produziram redução significante do edema facial, aumento da distância interincisal máxima ativa, redução do quadro álgico no grupo tratamento comparativamente ao grupo rotina. Esses dados reforçam a hipótese de que a DLM proposta foi efetiva contribuindo de maneira importante na recuperação do paciente submetido à cirurgia de EOA. / OBJECTIVE: To determine the effectiveness of standardized manual lymphatic drainage (MLD) maneuvers in reducing facial swelling, maximum interincisal active distance and pain of patients undergoing surgery for Alveolar Bone Grafting (ABG). METHODS: This study examined 51 individuals with repaired cleft lip and palate, aged 10 to 15 years old, who underwent ABG at the Hospital for Rehabilitation of Craniofacial Anomalies- USP, divided into two groups: treatment group (n = 29, 12 men and 17 women) and routine group (n = 22, 15 men and 7 women). In the treatment group MLD standardized maneuvers were performed differently from those of the group routine. In both groups evaluation of facial swelling was performed by measuring the distance from the ala nasi to the tragus (line 1) and the distance from the ala nasi to the inferior portion of the ear auricle (line 2), in the operated side, preoperatively, and at the second and the fourth postoperative (PO) day. The maximum active interincisal distance was measured during the same periods. The Pain Analog Scale (PAS) was applied at the first, second, third and fourth days after ABG. Additionally, patients from the treatment group, were asked about pain, relaxation and sleep after MLD therapy. RESULTS: There was a reduction of facial edema in the treatment group from the 2nd to 4th PO what was not observed the routine group. Interincisal distance increased between the 2nd and 4th PO in both groups. PAS evaluation has shown that patients from the treatment group present no pain already at 3rd PO. In the routine group this occurred only at 4th PO. All the subjects from treatment group reported decrease of pain, and patients reported felt more relaxed after the MLD, at the three postoperative evaluated. Many patients reported that MLD had a facilitative effect on inducing sleep during MLD. CONCLUSIONS: The standardized MLD maneuvers applied in the proposed manner produced significant reduction of facial swelling, increase of the maximum active interincisal distance, reduction of the pain in the treatment group as compared to the routine group.These Abstract data reinforce the hypothesis that the proposed MLD is a effective procedure for the recovery of the patients undergoing ABG surgery.