The theoretical model of Beratan and Onuchic predicts a large attenuation of ET rates through hydrogen bonds; however, the effect of individual hydrogen bond on electron transfer reaction has not been systematically studied. The organic complexes in this study are a series of crown ether/ammonium salt, which incorporate a redox partner on each component of the complex. The dimethoxynaphthalene redox donor was attached to the crown ether and a series of ammonium salts was synthesized which bear substituted quinone and naphthoquinone acceptor. The complexes characterization and preliminary electron transfer rate measurement were completed with UV/Vis and steady-state emission spectroscopy.

Cellulose nanocomposites offer interesting potential in terms of improved properties and new functionalities compared with microcomposites. Preparation from colloidal suspensions is promising, since high reinforcement content is possible and a wide range of constituents can be used. In the first study, the challenge is to form a stable suspension of well-dispersed carbon nanotubes (CNT) and nanofibrillated cellulose (NFC) in water and to prepare commingled high CNT content nanopaper structures by filtration. Various surfactants were used to modify CNT. The NFC was stabilized by charged carboxylate groups. A nonylphenol phosphate ester surfactant, NPPE, worked well for CNT and provided a stable and well-dispersed water suspension of CNT and NFC. Field emission scanning electron microscopy (FE-SEM), porosimetry and atomic force microscopy (AFM) were used to characterize nanopaper structure, and tensile properties were measured as well as surface resistivity. The processing route is water based and it is possible to prepare thin coatings as well as thicker films with a combination of low surface resistivity, flexibility in bending and high strength and toughness in tension.  As inspired by organo-modified layered silicates, the objective of the second study is to develop an environmentally friendly procedure for the surface modification of cellulose nanocrystals, CNC, using quaternary ammonium salts via adsorption. In order to obtain higher surface charge density on CNC, a new route is developed for preparation of CNC with carboxylic acid groups. Quanternary ammonium cations bearing alkyl, phenyl, glycidyl, and diallyl groups are used to modify CNC to render their surface more hydrophobic. The structure and surface hydrophobicity of unmodified and modified CNC as well as their dispersibility in organic solvent are characterized by AFM, FE-SEM, Fourier-transformed infrared spectroscopy (FT-IR), X-Ray analysis (XDR) and contact angle measurement (CAM). Future work will focus on surface-modified nanocelluloses in composite materials, in order to learn more about surface treatment effects on nanocomposite properties. / Nanokompositer från cellulosa har potential att ge starkt förbättrade egenskaper och ny funktionalitet jämfört med mikrokompositer. De ger även möjlighet till komposittillverkning från kolloidala suspensioner där man kan uppnå hög halt av förstärkningsfasen. Det är också möjligt att välja från en bred flora av lösliga och dispergerbara materialkomponenter. I första studien är utmaningen att skapa en stabil och väldispergerad suspension av kolnanorör (CNT) och nanofibrillerad cellulosa (NFC) i vatten för att genom filtrering framställa nanopapper med interpenetrerande CNT och NFC nätverk. Olika ytaktiva ämnen användes för att modifiera CNT. NFC stabiliserades genom laddade karboxylgrupper på ytan. En nonylfenol fosfatester, NPPE, fungerade bra för CNT och resulterade i en stabil och väldispergerad vattensuspension av CNT och NFC. FE-SEM, densitometri och AFM användes för att karakterisera nanopapperstruktur. Mekaniska egenskaper och ytresistivitet mättes. Processen för framställning av CNT/NFC nanopapper är vattenbaserade och det är möjligt att framställa tunna ytbeläggningar likväl som tjockare filmer. Dessa strukturer har en kombination av låg resistivitet, flexibilitet i böjning liksom hög hållfasthet och seghet i dragbelastning.  Syftet med den andra studien är att utgå från organo-modifierade skiktade silikater (leror) för att utveckla en miljövänlig ytmodifieringsmetod för nanocellulosa. För att öka ytladdningstätheten på CNC (nanokristaller från cellulosa) utvecklas ett nytt sätt att skapa karboxylgrupper på ytan. Kvarternära ammoniumsalter med alkyl, fenyl, glycidyl och diallylgrupper används för att göra ytan på CNC mer hydrofob. Ytans struktur och hydrofoba karaktär, liksom dispersionsegenskaper i organiska lösningsmedel, karakteriseras med hjälp av AFM, FE-SEM, FT-IR, XDR och kontaktvinkelmätning. Fortsatt arbete kommer att fokusera på ytmodifierad cellulosa i kompositmaterial, för att utveckla förståelsen för effekter av ytmodifiering på nanokompositers egenskaper / <p>QC 20120302</p>

Indiana University-Purdue University Indianapolis (IUPUI) / Both quaternary ammonium bromide (QAB) and furanone derivatives were synthesized, characterized and formulated into dental resin composites for improved antibacterial properties. Compressive strength (CS) and S. mutans viability were used to evaluate the mechanical strength and antibacterial activity of the restoratives. The effects of chain length, loading, saliva and aging on CS and S. mutans viability were investigated. Chapter 2 describes how we studied and evaluated the formulated antibacterial resin composites by incorporating the synthesized QAB-containing oligomers into the formulation. The results show that all the QAB-modified resin composites showed significant antibacterial activity and mechanical strength reduction. Increasing chain length and loading significantly enhanced the antibacterial activity but dramatically reduced the CS as well. The 30-day aging study showed that the incorporation of the QAB accelerated the degradation of the composite, suggesting that the QAB may not be well suitable for development of antibacterial dental resin composites or at least the QAB loading should be well controlled. Chapter 3 describes how we studied and evaluated the formulated antibacterial resin composite by incorporating the synthesized furanone derivative into the formulation. The results show that the modified resin composites showed a significant antibacterial activity without substantially decreasing the mechanical strengths. With 5 to 30% addition of the furanone derivative, the composite kept its original CS unchanged but showed a significant antibacterial activity with a 16-68% reduction in the S. mutans viability. Further, the antibacterial function of the new composite was found not to be affected by human saliva. The aging study indicates that the composite may have a long-lasting antibacterial function. In summary, we have developed a novel QAB- and furanone-containing antibacterial system for dental restoratives. Both QAB- and furanone-modified resin composites have demonstrated significant antibacterial activities. The QAS-modified experimental resin composite may not be well suitable for development of antibacterial dental resin composites due to its accelerated degradation in water unless the QAB loading is well controlled. The furanone-modified resin composite shows nearly no reduction in mechanical strength after incorporation of the antibacterial furanone derivative. It appears that the furanone-modified resin composite is a clinically attractive dental restorative that can be potentially used for long-lasting restorations due to its high mechanical strength and permanent antibacterial function.

Cette thèse décrit la Chimie Covalente Dynamique (CCD) des échanges imine/imine, Knoevenagel/imine et Knoevenagel/Knoevenagel. La L-proline est un excellent organocatalyseur pour la formation de Bibliothèques Covalentes Dynamiques (BCDs). Cependant, l’interconversion entre des dérivées Knoevenagel de l’acide diméthylbarbiturique et des imines se déroule rapidement sans catalyseur. Une nouvelle classe de CCD basée sur des échanges par substitutions nucléophiles (SN2/SN2’) entre des sels d’ammonium quaternaires et des amines tertiaires est développée, impliquant la catalyse par l’iodure. Les réactions d’échange entre des sels de pyridinium et un dérivé de pyridine génèrent des liquides ioniques dynamiques. Enfin, la sélection cinétique et thermodynamique de la formation d’imines dans la CCD est réalisée en solution aqueuse e ten solvant organique. / This thesis describes the dynamic covalent chemistry (DCC) of imine/imine, Knoevenagel/imine, and Knoevenagel/Knoevenagel exchange. L-proline is shown to be an excellent organocatalyst to accelerate the formation of dynamic covalent libraries (DCLs). The interconversion between Knoevenagel derivatives of dimethylbarbituric acid and imines is found to occur rapidly in the absence of catalyst. A new class of DCC based on nucleophilic substitution (SN2/SN2’) component exchange between quaternary ammonium salts and tertiary amines is developed, by the use of iodide as a catalyst. The exchange reactions between pyridinium salts and a pyridine derivative generate dynamic ionic liquids. Finally, kinetic and thermodynamic selection of imine formation in a DCC is perfomed in aqueous solution and organic solvent.