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Amyloid fibrils results from a type of ordered polypeptide aggregation that is associated with ailments such as Alzheimer's disease (AD). Annually, millions of people in the United States alone develop and die from AD. Therefore, it is necessary to understand not only the process of amyloid formation, but also the causes of this specific type of aggregation. This study used ABeta(25-35) since it is a fragment of the Alzheimer?s peptide that behaves like the full length peptide found in patients with AD. To study the process of amyloid formation, several methods were used so that a more complete picture of the stepped aggregation process could be realized. Several oligomeric species were detected and described many of which could not have been observed without using the complete battery of methods utilized here. The oligomeric species detected included a novel 'rolled sheet' that appeared to be the immediate precursor of amyloid fibrils, and two supermolecular species that appear after amyloid fibrils were formed. In determining the causes of amyloid formation, two significant discoveries were made. First, by partial sequence randomization, truncation, and Ala scanning mutagenesis, the critical amyloidogenic region of ABeta(25-35) was found to be residues 30-35. This critical core region is important because it is thought to be the region that initiates amyloid formation, therefore knowing the residues involved in the region is a useful tool for developing methods of fibril formation prevention. Second, by inserting all naturally occurring amino acids into position 34 of ABeta(25-35), three distinct classes of variants were observed and the effect of several physiochemical properties on amyloidosis were examined. Hydrophobicity, solubility, and ?-strand propensity were found to affect aggregation to the greatest extent. Also within these two studies, our results suggest that early oligomers are the cytotoxic species as opposed to amyloid fibrils or other larger macromolecular assemblies.

Due to the successful commercialization of lithium-ion batteries (LIBs), there is a growing interest in developing new battery materials with beneficial electrochemical properties. However, the uneven distribution of lithium resources and the low abundance of lithium in the earth crust are the main obstacles for further development and large-scale production of LIBs. Sodium-ion batteries (SIBs), an alternative that can partly meet the energy storage challenges, are getting attentions of researchers due to the wide availability and lower cost of sodium resources. Nevertheless, the conventional liquid electrolytes of either LIBs or SIBs composed of fluorinated salts dissolved in volatile organic solvents, posing serious safety issues due to the instability of the salts and flammability of the solvents. There is an urge to develop new fluorine-free electrolytes with improved physicochemical and electrochemical properties. In this context, the conventional fluorinated salts should be replaced with fluorine-free salts and the flammable solvents should be substituted with non-flammable solvents. There are a number of strategies to develop high-performant electrolytes including ambient-temperature ionic liquids (ILs), organic ionic plastic crystals (OIPCs) and highly concentrated electrolytes (HCEs) utilizing new salts and solvents. In this thesis, novel phosphorus-based ionic materials and electrolytes are introduced and their properties are thoroughly investigated. In the first part (Paper I), fluorine-free NaDEEP salt and TEOP solvent are employed to make “solvent-in-salt” (SIS) sodium electrolytes, also known as HCEs. Unexpectedly, the addition of TEOP solvent lead to an increase in the oxidation stability of the SIS electrolytes. In addition, an unusual ionic conductivity behavior is found – the ionic conductivities of Na electrolytes increase with increasing salt concentration. The “salt-rich” and “solvent-rich” phases formed within the electrolytes are investigated using multinuclear liquid-state NMR spectroscopy and NMR diffusometry. In the second part (Paper II), a series of orthoborate-based ionic materials, specifically OIPCs, containing phosphonium/ammonium cations are prepared to compare with the popular fluorine-free, bis(oxalato)borate (BOB) salts. The tetrabutyl phosphonium bis(glycolato)borate ([P4444][BGB]) OIPC displays much higher decomposition temperature than the structural analogous [P4444][BOB] IL. The crystal structures of LiBGB and NaBGB salts are resolved using single-crystal X-ray diffraction analysis. Unlike LiBOB, the BGB-based salts revealed excellent moisture stability over an extended time of up to 8-weeks air exposure. Multinuclear solid-state NMR spectroscopy indicates weaker cation-anion interactions in phosphonium-based salts than the ammonium-based ones. Finally, in the third part (Paper III), two-component and three-component eutectic electrolytes, composed of pyrrolidinium saccharin (PySc), lithium saccharin (LiSc) and/or [P4444][BGB] salt. The resulting mixtures showed significantly lower melting temperatures than the neat salts. The physicochemical and thermal properties of these salts are thoroughly investigated and discussed.

One of the major directions of research in the area of materials science is to impart multifunctionalities to materials. Carbon stands on the top of the list to provide various multifunctional materials. It exists in all dimensions, zero (fullerene), one (carbon nanotube, CNT), two (graphene) and three (graphite) dimensions are very well-known for their versatility in various studies. They are also used in various applications in nanoelectronics, polymer composites, hydrogen production and storage, intercalation materials, drug delivery, sensing, catalysis, photovoltaics etc. Electrical conductivity of carbon can be tuned from insulator (diamond) to semiconductor (graphene) to conductor (graphite) with varying band gap. The main reason for this versatility and varied properties is that carbon can be involved in different hybridizations. Graphene, a single layer of graphite has fascinated the world during the last several years culminating in a Nobel prize for Physics in 2010. The present study is an attempt to understand the physicochemical and electrochemical properties of graphite oxide and its reduced form. Graphene oxide (GO) possesses oxygen containing functional groups such as carbonyl, carboxyl and epoxy groups distributed very randomly in the extended graphene sheet which makes it ionically conducting and electrically insulating. The AFM images of single layer of graphite (graphene) obtained from micromechanical cleavage method and that of EGO are shown in figure 1. EGO is a layered material similar to graphite and can form very stable aqueous colloids over a wide pH range of 2-11. The stability of the colloid is due to electrostatic repulsive interactions between the functional groups. EGO behaves like a molecule due to its thickness (~1 nm) and like a particle due to its two dimensional nature (lateral size can vary from nm to few microns). It behaves as amphiphilic molecule having both hydrophilic and hydrophobic nature. Figure 1d shows the STM image of EGO which clearly indicates oxidized and unoxidized regions which will impart hydrophilic and hydrophobic regions respectively. Figure 1: AFM image of (a) graphene (b) EGO. STM image of (c) HOPG and (d) EGO. The present work is related to exploring EGO as a multifunctional material. Both hydrophilic and amphiphilic nature is explored for various studies. Reduced GO (rGO) is synthesized from EGO by assembling at different interfaces (solid-liquid and liquid-air) followed by reduction. Since EGO is hydrophilic, it is brought to the air-water interface with the help of a surfactant (CTAB) through electrostatic interactions. It is reduced chemically by hydrazine vapour to rGO and electrochemically by assembling EGO on gold through electrostatic interactions between EGO and amine groups of cystamine (figure 2). The reduction process is followed by AFM, UV-Visible and in-situ Raman spectroelectrochemistry. Figure 2: Schematic of EGO self assembly, cyclic voltammogram showing electrochemical reduction and schematic for in-situ Raman spectroelectrochemistry. The next section deals with composites of EGO and polymers. EGO/polyaniline (PANI) composite is formed by electrochemical polymerization under applied surface pressure. The in-situ electrochemical polymerization of aniline in the sub-phase of Langmuir-Blodgett trough under applied surface pressure in presence of EGO at the air-water interface leads to preferential orientation of PANI in the polaronic form. This is followed by electrochemistry and Raman spectroscopy. Figure 3 shows differential pulse voltammograms of EGO/PANI obtained under two different conditions. Externally polymerized sample shows three redox peaks at 0.086/0.064 V (A/A‟), 0.390/0.430 V (B/B‟) and 0.520/0.560 mV (C/C‟) which correspond to leucoemaraldine/emaraldine, quinone/hydroquinone and emaraldine/pernigraniline redox states respectively. The peak at C/C‟ vanishes when aniline is polymerized in-trough under applied surface pressure. This implies that oxidation of emaraldine to pernigraniline becomes difficult when sample is prepared in-trough. The Raman spectroscopy clearly reveals the preferential orientation of PANI in planar polaronic structure. Figure 3. Differential pulse voltammograms for EGO/PANI complex obtained through external polymerization (black) and in-trough polymerization (red). In the next part, EGO is used as a proton conducting material for polymer electrolyte membrane fuel cell (PEMFC). EGO possesses hydrophilic and hydrophobic regions similar to nafion (sulfonated tetrafluoroethylene based fluoropolymer-copolymer) and hence it can act as a good ionically conducting membrane. EGO is incorporated in poly(vinyl alcohol) (PVA) matrix and used in the present studies. The ionic conductivity increases from 10 μS cm-1 to 370 μS cm-1 when EGO content is increased from 1wt% to 7wt% in PVA matrix. Power densities of 25 and 90 mW cm-2 are obtained for PVA and PVA/EGO membranes in H2-O2 fuel cell at 40 0C respectively. In the next section, EGO is used as receptor for simultaneous electrochemical detection of heavy metal ions such as Cd, Pb, Cu and Hg with detection limit of 5 μM, 1 pM, 5 μM and 5 μM respectively. During the process it is observed that the EGO/PbO composite can give rise to detection limit of 10 nM for arsenic. Along with detection, EGO can also be used as an effective adsorbent for inorganics (metal ions) as well as organics (dye molecules). EGO behaves as good adsorbent for heavy metal ions and cationic dyes and rGO adsorbs anionic dyes effectively. Spectroscopic techniques are used to understand the interactions between adsorbent and adsorbates. The thesis is presented as follows: Chapter 1 gives general introduction about graphene and graphite oxide with particular emphasis on the latter one. Chapter 2 gives details on the experimental methods followed, along with schematics for various adsorption processes. Chapter 3 focuses on assembling EGO at interfaces (solid-liquid and liquid-air) followed by reduction with chemical and electrochemical methods. Chapter 4 explores EGO as an amphiphilic material where EGO is assembled at air-water interface with anilinium and subsequent electropolymerization to EGO/PANI composites. EGO/PVA composite is used as electrolyte for PEMFC. Chapter 5 explores EGO as receptor for heavy metal ion detection (Cd, Pb, Cu and Hg). Chapter 6 deals with EGO as adsorbent for adsorption of inorganics (metal ions) as well as organics (dye molecules). This is followed by summary and conclusions. The appendix section gives details on the studies on preparation of exfoliated graphite with various metal ion intercalation. The covalent functionalization of EGO with metal phthalocyanines and its assembly at air-water interface forms second part of the appendix. (For figures pl see the abstract pdf file)

From the Proceedings of the 1972 Meetings of the Arizona Section - American Water Resources Assn. and the Hydrology Section - Arizona Academy of Science - May 5-6, 1972, Prescott, Arizona / The need for increased control of seepage from both natural and artificial small ponds and lakes has become more apparent with the increased frequency of their construction and use on the farm, ranch, and in recreational urban use. Seepage control methods are also becoming more numerous. Unfortunately, comparisons as to effectiveness, longevity and costs are not readily available. This paper investigates some control techniques being used in this region and evaluated them according to the above criteria. Emphasis was on the use of available physiochemical methods other than rubber membranes and concrete liners. Examples of the types of controls in use include plastic, soil compaction aids, hydrophobic chemicals and monovalent cation applications, such as sodium chloride. Some examples of the use of these methods in Arizona are shown and the results of some field comparison tests conducted using 8 x 8 square foot double -ringed infiltrometers presented. Recommendations are made of additional research that should be undertaken to improve the technology of the control of seepage losses.

Le procédé de mise en forme des tôles métalliques, généralement oxydées, par emboutissage est en pleine évolutionpour répondre à de nouveaux besoins : intervalles de tolérances dimensionnelles de plus en plus étroits, productionen grande série à faible coût, apparition de nouvelles nuances de matériaux, souci écologique. La réussite d’une telleopération est prédominée par le contrôle du frottement au niveau du contact entre tôle à former et outil enmouvement relatif. Pour ce faire, nous proposons dans cette thèse de fonctionnaliser la surface de la tôle en ygreffant des molécules organiques auto-assemblées, par simple immersion dans une solution contenant les moléculesréactives. Le couple métal/molécule retenu pour cette étude est un substrat massif de cuivre pur avec des moléculesd’acides alkylphosphoniques (CnH2n+1PO(OH)2) dans le but d’établir une corrélation entre les propriétésphysicochimiques des films ainsi formés et leur comportement tribologique. La réponse en frottement a été étudiéepar deux moyens de simulation expérimentale des conditions de contact (tribomètres bille/plan et étirage-plan). Nousavons considéré l’influence des trois facteurs de préparation de substrat suivant μ la nature de surface juste avant safonctionnalisation (présence d’une couche d’oxyde ou d’hydroxyde), le nettoyage de surface aux ultrasons après safonctionnalisation (élimination des espèces physisorbées) et la longueur de chaîne alkyle de la moléculeorganophosphonique (n=4, 12 et 16). Bien que la formulation de cette fonctionnalisation soit simple (élaborée àpartir d’une seule molécule), les techniques d’investigation de surface (PM-IRRAS, XPS, électrochimie, MEB,…)montrent que les films auto-assemblés sont constitués d’une bicouche de bonne qualité de greffage et de propriétésanticorrosion. Cette bicouche est composée d’une première monocouche de molécules chimisorbées à la surface (ouSAM) sur laquelle est déposée une deuxième couche d’amas physisorbés. D’autre part, notre étude a montréégalement que les amas physisorbés ont un rôle primordial dans le comportement tribologique du film auto-assemblé(abaissement et stabilité du coefficient de frottement et prévention contre le grippage). / Sheet metal forming processes are quickly evolving to meet new requirements of deep drawing such as: continuousminimization of dimensional tolerances intervals, cost efficiency at mass production, appearance of new materialstypes, environmental concern. The success of such operation is predominated by controlling friction at the contactbetween the metal sheet and forming tool in relative motion. In the present work, we propose to functionalize themetal sheet surface using grafting of self-assembled organic molecules by simple immersion in a solution containingthe reactive molecules. Consequently, thin film of alkylphosphonic acid (CnH2n+1PO(OH)2) was grafted on copperoxide substrate in order to establish a correlation between the physicochemical properties of the films andtribological behavior. Frictional response was studied by two experimental means of contact conditions (stripdrawing testing and ball-on-plane tribometer). The influence of three factors for the preparation of substrate wasconsidered. Firstly, the nature of its surface just before functionalization including the presence of an oxide orhydroxide layer was studied. Then, the ultrasonic surface cleaning after functionalization (removal physisorbedspecies) and finally, the alkyl chain length of the organophosphonic molecule (n = 4, 12 and 16). Although theformation of this functionalization is simple (made from a single molecule), the surface investigation techniques(PM- IRRAS , XPS, electrochemistry , SEM, .., etc.) show that self-assembled films consist of a bilayer with a goodgrafting quality and anticorrosion properties. The bilayer is composed of a first monolayer of molecules chemisorbedon the surface (or SAM) on which a second layer of physisorbed species is deposited. Furthermore, this study alsoshowed that the physisorbed species have a key role in the tribological behavior of self-assembled film (lower andstable friction coefficient and high resistance to galling).