This dissertation describes a structural investigation of hyaluronan (HA) with neutron scattering techniques. HA is a natural biopolymer and one of the major components of the extracellular matrix, synovial fluid, and vitreous humor.  It is used in several biomedical applications like tissue engineering, drug delivery, and treatment of osteoarthritis. Although HA is extensively studied, very little is known about its three-dimensional conformation and how it interacts with ions and other molecules. The study aims to understand the bulk structure of a cross-linked HA hydrogel, as well as the conformational arrangement of HA at solid-liquid interfaces. In addition, the structural changes of HA are investigated by simulation of physiological environments, such as changes in ions, interactions with nanoparticles, and proteins etc. Small-angle neutron scattering and neutron reflectivity are the two main techniques applied to investigate the nanostructure of hyaluronan in its original, hydrated state. The present study on hydrogels shows that they possess inhomogeneous structures best described with two correlation lengths, one of the order of a few nanometers and the other in the order of few hundred nanometers. These gels are made up of dense polymer-rich clusters linked to each other. The polymer concentration and mixing governs the connectivity between these clusters, which in turn determines the viscoelastic properties of the gels. Surface-tethered HA at a solid-liquid interface is best described with a smooth varying density profile. The shape of this profile depends on the immobilization chemistry, the deposition protocol, and the ionic interactions. HA could be suitably modified to enhance adherence to metal surfaces, as well as incorporation of proteins like growth factors with tunable release properties. This could be exploited for surface coating of implants with bioactive molecules. The knowledge gained from this work would significantly help to develop future biomaterials and surface coatings of implants and biomedical devices.

Die hier vorliegende Studie stellt die Früh- und Langzeitergebnisse der chirurgischen Vorhofablation zur Behandlung des ischämischen Vorhofflimmerns (VHF) in Kombination mit einer aortokoronaren Bypass-Anlage vor. Dabei wurden die epikardiale Pulmonalvenenisolation mittels Radiofrequenzenergie (RF) und die endokardiale Kryoablation inklusive einer Box-Läsion und Mitralisthmuslinie miteinander verglichen. Im Zeitraum von 2002 bis 2009 wurden die prä- und postoperativen Daten von 262 Patienten mit paroxysmalem oder lang-persistierendem VHF prospektiv erhoben und anschließend eine Nachbeobachtung von durchschnittlich 2,30 Jahren durchgeführt. Die Kryoablation war im Vergleich zur RF-Ablation mit einer signifikant höheren perioperativen Invasivität und Morbidität verbunden. Die Operations- und Ischämiezeit sowie die postoperative intensivmedizinische Betreuung waren nach der Kryoablation signifikant länger. Die Rate an Schrittmacherimplantationen (4,8 % vs. 0,0 %), kardialen bzw. zerebralen Komplikationen (22,9 % vs. 12,3 %) und die Krankenhausmortalität (8,4 % vs. 2,2 %) lagen ebenfalls signifikant höher. Hingegen waren die Langzeitergebnisse ohne signifikante Unterschiede zwischen den Ablationsmethoden. Sowohl das Überleben (81,9 % vs. 86,0 %) als auch die Konversionsrate in den Sinusrhythmus (55,6 % vs. 61,5 %), die Lebensqualität der Patienten und die Komplikations- und Reinterventionsraten zeigten im Langzeitverlauf vergleichbare Ergebnisse. Auf der Basis der oben erhobenen Befunde kann die endokardiale Kryoablation nicht als Standardverfahren zur Therapie des paroxysmalen und lang-persistierenden ischämischen VHFs begleitend zu einer aortokoronaren Bypass-Anlage empfohlen werden. Die epikardiale RF-Ablation ist hier aufgrund der geringeren operativen Invasivität bei vergleichbaren Früh- und Langzeitergebnissen der endokardialen Ablation vorzuziehen.

Cellulose is one of the most abundant biopolymers found in nature. Cellulose based derivatives have a number of advantages including recyclability, reproducibility, biocompatibility, biodegradability, cost effectiveness and availability in a wide variety of forms. Due to the benefits of cellulose based systems, this research study was aimed at developing novel cellulosic nanoparticles with potential pharmaceutical and personal care applications. Two different cellulosic systems were evaluated, each with its own benefits and proposed applications. The first project involves the synthesis and characterization of polyampholyte nanoparticles composed of chitosan and carboxymethyl cellulose (CMC), a cellulosic ether. EDC carbodiimide chemistry and inverse microemulsion technique was used to produce crosslinked nanoparticles. Chitosan and carboxymethyl cellulose provide amine and carboxylic acid functionality to the nanoparticles thereby making them pH responsive. Chitosan and carboxymethyl cellulose also make the nanoparticles biodegradable and biocompatible, making them suitable candidates for pharmaceutical applications. The synthesis was then extended to chitosan and modified methyl cellulose microgel system. The prime reason for using methyl cellulose was to introduce thermo-responsive characteristics to the microgel system. Methyl cellulose was modified by carboxymethylation to introduce carboxylic acid functionality, and the chitosan-modified methyl cellulose microgel system was found to be pH as well as temperature responsive. Several techniques were used to characterize the two microgel systems, for e.g. potentiometric and conductometric titrations, dynamic light scattering and zeta potential measurements. FTIR along with potentiometric and conductometric titration was used to confirm the carboxymethylation of methyl cellulose. For both systems, polyampholytic behaviour was observed in a pH range of 4-9. The microgels showed swelling at low and high pH values and deswelling at isoelectric point (IEP). Zeta potential values confirmed the presence of positive charges on the microgel at low pH, negative charges at high pH and neutral charge at the IEP. For chitosan-modified methyl cellulose microgel system, temperature dependent behaviour was observed with dynamic light scattering. The second research project involved the study of binding interaction between nanocrystalline cellulose (NCC) and an oppositely charged surfactant tetradecyl trimethyl ammonium bromide (TTAB). NCC is a crystalline form of cellulose obtained from natural sources like wood, cotton or animal sources. These rodlike nanocrystals prepared by acid hydrolysis of native cellulose possess negatively charged surface. The interaction between negatively charged NCC and cationic TTAB surfactant was examined and it was observed that in the presence of TTAB, aqueous suspensions of NCC became unstable and phase separated. A study of this kind is imperative since NCC suspensions are proposed to be used in personal care applications (such as shampoos and conditioners) which also consist of surfactant formulations. Therefore, NCC suspensions would not be useful for applications that employ an oppositely charged surfactant. In order to prevent destabilization, poly (ethylene glycol) methacrylate (PEGMA) chains were grafted on the NCC surface to prevent the phase separation in presence of a cationic surfactant. Grafting was carried out using the free radical approach. The NCC-TTAB polymer surfactant interactions were studied via isothermal titration calorimetry (ITC), surface tensiometry, conductivity measurements, phase separation and zeta potential measurements. The major forces involve in these systems are electrostatic and hydrophobic interactions. ITC and surface tension results confirmed two kinds of interactions: (i) electrostatically driven NCC-TTAB complexes formed in the bulk and at the interface and (ii) hydrophobically driven TTAB micellization on the NCC rods. Conductivity and surface tension results confirmed that the critical micelle concentration of TTAB (CMCTTAB) shifted to higher values in the presence of NCC. Phase separation measurements allowed us to identify the formation of large aggregates or hydrophobic flocs depending on the TTAB concentration. Formation of NCC-TTAB complexes in aqueous solutions was confirmed by a charge reversal from negative to positive charge on the NCC rods. The effect of electrolyte in shielding the negative charges on the NCC was observed from ITC, surface tensiometry and phase separation experiments. Several mechanisms have been proposed to explain the above results. Grafting of PEGMA on the NCC surface was confirmed using FTIR and ITC experiments. In phase separation experiments NCC-g-PEGMA samples showed greater stability in the presence of TTAB compared to unmodified NCC. By comparing ITC and phase separation results, an optimum grafting ratio (PEGMA : NCC) for steric stabilization was also proposed.

Soil salinity affects over 20% of the worlds irrigated land. Potato (Solanum tuberosum L.), the most important vegetable crop worldwide, is relatively salt sensitive. However, relatively little work has been done on salt tolerance of the potato plant. This thesis investigated the methodology of treatment application and scion/rootstock effects on subsequent salt stress responses of four contrasting potato genotypes: Norland, 9506, 9120-05 [ABA-deficient mutant], and 9120-18 [ABA-normal sibling] grown hydroponically in sand. The effect of incremental salt stress were studied, using NaCl, CaCl2 and combined NaCl + CaCl2 pre- treatments as well as varying methods of ABA application with a specific focus on the role of rootstock and scion. Physiological responses of various potato genotypes to salt stress differed depending on how the salt stress was applied. An incremental salt stress regime was able to more effectively differentiate genotypes based on salt stress resistance and greater salt tolerance compared to a sudden salt shock. Generally, the ability to produce ABA was positively related to the degree of salt stress resistance, with higher ABA levels induced under incremental salt stress treatments compared to salt shock. The method of ABA application also had a marked effect on potato responses to salt stress. Slowly increasing concentrations of exogenous ABA maintained growth rates, enhanced root water content and induced more lateral shoot growth compared to a single ABA dose. The degree of salt tolerance induced by the grafted rootstock was primarily modulated by salt acclimation and was manifested in the scion as increased water content, stem diameter, dry matter accumulation, stomatal conductivity, and osmotic potential and was associated with reduced leaf necrosis. Using the salt-resistant 9506 line as a scion also significantly increased root fresh and dry weight and stem diameter as well as root water content of salt-sensitive ABA-deficient mutant rootstocks. Exogenous ABA appeared to enhance plant water status via the roots under salt stress beyond that of grafting alone. This was verified by more positive stomatal conductivity and greater upward water flow in ABA treated grafted and non-grafted plants as compared to the absence of upward water flow in non-treated grafted plants as measured via micro NMR imaging. NaCl pre-treatment produced greater salt stress resistance compared to pre-treatment with CaCl2 and was associated with a specific Na+ ion effect rather than a non-specific EC-dependent response. However, the presence of both ABA and CaCl2 appears to be necessary in order to enhance Na+ exclusion from the shoot and increases the K+/Na+ ratio.

The compound 2,6-anthracenedicarboxylic acid is used as a comonomer for the synthesis of poly(ethylene terephthalate). The resulting copolymers are characterized and further functionalized by Diels-Alder grafting or crosslinking through the anthracenate unit. Diels-Alder reaction is used to graft small molecules and oligomers endcapped with maleimide as dienophiles on to poly(ethylene terephthalate-co-2,6-anthracenedicarboxylate),PET-co-A. Maleimide-capped poly(ethylene glycol) is grafted onto PET-co-A to improved its hydrophilicity. 2,6-Anthracenedicarboxylic acid is also incorporated into the known liquid crystalline polymer, LCP, poly(4-oxybenzoate-co-1,4-phenylene isophthalate), HIQ40. The resulting copolymer, poly(4-oxybenzoate-co-1,4-phenylene isophthalate-co-2,6-phenylene anthracenate), HIQ40-co-A, shows LCP behavior. These HIQ40-co-A copolymers are grafted with maleimide end-capped monomers and polymers andcrosslinked with bismaleimides through a Diels-Alder mechanism.

Surface grafting and modification of poly(acrylic acid) (PAA) were performed on nylon 6,6 carpet fibers to achieve permanent stain and soil resistance. PAA was grafted to nylon and modified with 1H, 1H-pentadecafluorooctyl amine (PDFOA) using an amidation agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). The first goal was to optimize acrylamide modification of PAA in solution. Aqueous reactions with taurine, hydroxyethyl amine, and butyl amine progressed ~100%, while PDFOA reactions in MeOH progressed ~80%. Reaction products precipitated at 77% butyl or 52% PDFOA acrylamide contents. The second goal was to optimize the PAA grafting process. First, PAA was adsorbed onto nylon 6,6 films. Next, DMTMM initiated grafting of adsorbed PAA. PAA surface coverage was ~78%, determined by contact angle analysis of the top 0.1-1 nm and x-ray photoelectron spectroscopy (XPS) analysis of the top 3-10 nm. The third goal was to modify PAA grafted nylon films with butyl amine and PDFOA. Randomly methylated beta-cyclodextrin (RAMEB) solubilized PDFOA in water. Contact angle detected ~ 100% surface reaction for each amine, while XPS detected ~77% butyl amine (H2O) and ~50% for PDFOA (MeOH or H2O pH=7) reactions. In H2O pH=12, the PDFOA reaction progressed ~89%, perhaps due to greater efficiency, access and solubility. The fourth goal was to perform surface depth profiling via angle-resolved XPS analysis (ARXPS). The PAA surface coverage from contact angle and XPS was confirmed. Further, adsorbed PAA was thicker than grafted PAA, supporting the theory that PAA adsorption occurs in thick layers onto nylon followed by DMTMM-activated spreading and grafting of thinner PAA layers across the surface. The PDFOA reaction in MeOH produced a highly fluorinated but thin exterior and an unreacted PAA interior. The PDFOA reaction in H2O pH=12 produced a completely fluorinated exterior and highly fluorinated interior. Thus surface modification levels from contact angle and XPS were confirmed. The final goal was to PAA-graft and PDFOA-modify nylon 6,6 fabrics and carpets. PDFOA modification achieved significant water and oil repellency. Stainblocking was slightly improved for ionized PAA-g-nylon and greatly improved for PDFOA-modified PAA-g-nylon. However, traditional stainblockers may be necessary to completely prevent dye penetration into carpet tufts.

We develop, characterize, and apply novel solvent systems for enhanced separations. The field of separations has long been explored by chemical engineers. One way to optimize separations is through solvent manipulation. Through molecular design, smart solvents can be created which accomplish this task. Smart solvents undergo step or gradual changes in properties when activated by a stimulus. These property changes enable unique chemistry and separations. This thesis explores the application of two different types of smart solvents: switchable and tunable solvents. First we show that a neutral liquid can react with carbon dioxide and be switched into an ionic liquid which can then be thermally reversed back to its molecular form. Each form that the solvent takes has unique properties that can be structurally tuned to span a large range. We also look at a tunable solvent system based on polyethylene glycol/dioxane that is initially homogeneous, but induced to a heterogeneous system through carbon dioxide pressurization. Finally, we look at the advantage of using carbon dioxide as a co-solvent that is easily removed post-reaction for the grafting of silanes onto polyolefin backbones.

As a low cost natural polymer, starch is widely used in paper, food, adhesive, and many other industries. In order to improve the performance of starch, crosslinking is often conducted either in the processes of starch modification or during the application processes. Many crosslinkers have been developed in the past for crosslinking starch. Ammonium zirconium carbonate (AZC) is one of the common crosslinkers for crosslinking starch in aqueous solutions, having been widely used as a starch crosslinking agent in paper surface coating for more than 20 years. However, the mechanisms of starch crosslinking with AZC have not been well studied. In order to optimize the crosslinking chemistry of starch and find new paths for the utilization of starch in papermaking, a better understanding of the starch crosslinking mechanism is necessary. This thesis focuses on the fundamental study of starch crosslinking in an aqueous solution and its applications in fiber surface grafting, filler modification, and starch nanoparticle formation. Particularly, the thesis contains three major parts: (1) Mechanism study of starch crosslinking induced by AZC: In this thesis, the crosslinking (or gelation) kinetics of starch/AZC blends were investigated by using rheological measurements. The evolution of viscoelastic properties of AZC solutions and the AZC-starch blends was characterized. It was found that for both AZC self-crosslinking and AZC-starch co-crosslinking, the initial bond formation rate and the gel strength had a strong power law relationship with the concentrations of both AZC and starch. It is suggested that the development of the crosslinking network is highly dependent on the AZC concentration, while the starch concentration effect is less significant. It was determined that the activation energy of AZC self-crosslinking was approximately 145-151 kJ/mol, while the activation energy of AZC-starch co-crosslinking was 139 kJ/mol. (2) Fiber and filler modifications with starch and crosslinkers: Besides reacting with starch, AZC can react with cellulose which also contains hydroxyl groups. Theoretically, it is possible to use AZC as a crosslinker / coupling agent to graft starch onto cellulose fibers. It is believed that the grafted starch on fiber surfaces can improve the fiber bonding capability. In this thesis, a facile method to graft starch onto cellulose fiber surfaces through the hydrogen bond formation among cellulose, starch and AZC was developed. Compared with the paper sheets made of fibers with an industry refining level (420 ml CSF), the paper sheets made of fibers with a much lower refining degree but with grafted starch showed higher paper strengths, including the tensile strength, stiffness and z direction tensile; meanwhile, a faster drainage rate during web formation could also be achieved. Not only can the fiber-fiber bonding be improved by grafting starch onto fiber surfaces, but the filler-fiber bonding can also be improved if starch can be effectively coated on the filler surface. This concept has been supported by the early studies. In this thesis, the effects of the crosslinking of starch in the filler modification for the papermaking application were also studied. (3) Mechanism of starch nanoparticle formation during extrusion with crosslinkers: It was reported that starch crosslinking could facilitate the reduction of starch particle size during reactive extrusion. However, the mechanism of the particle size reduction by starch crosslinking was not illustrated. The reason that the crosslinking can cause the particle size reduction of starch during extrusion is fundamentally interesting. In this thesis, the mechanism of starch particle size reduction during extrusion with and without crosslinkers was investigated by identifying the contributions of thermal and mechanical effects. The effects of extrusion conditions, including temperature, screw speed, torque, starch water content and crosslinker addition, on the particle size were studied. It was found that the addition of crosslinkers could significantly increase the shear force (torque), and consequently facilitate the reduction of the particle size. The results indicate that for extrusion without a crosslinker, the starch particle size decreased with the increase of temperature. At 100 degree Celsius, the starch particles with a size of 300 nm could be obtained. With the addition of appropriate crosslinkers (glyoxal), the starch particle size could be reduced to around 160 nm, even at a lower extrusion temperature of 75 degree Celsius .

This thesis focuses on the development of new compounds or new processes that are more environmentally friendly and economical than those currently in use. The decomposition of hydrazine, a well established liquid rocket fuel for both the aerospace and defense industries, to the product ammonia is studied. Control of this reaction will allow hydrazine to be used as a propellant for both chemical and electric propulsion. From this a dual stage thruster will be developed that will be more efficient than current systems decreasing the amount of propellant needed and allowing for either a larger mission payload or a longer duration of individual missions. Hydrazine, while beneficial and well established, is also highly toxic, so other work in this thesis focuses on the synthesis of the novel molecule 1,1-dimethyl-2-[2-azidoethyl]hydrazine or DMAEH and its hydrazone intermediate 1,1-dimethyl-2-[2-azidoethyl]hydrazone or De-DMAEH as less toxic hydrazine replacements. Novel "switchable" ionic liquids have been investigated in this research. These are solvents that can change from molecular liquids to ionic liquids and back, simply with the addition or removal of CO₂ from the system. They can be used for a variety of applications, including as solvents for a reaction and separation system. Due to the recyclable nature of these solvents, waste is decreased making their development and implementation both environmentally and economically beneficial. Finally, the grafting reaction of vinyl silanes onto a hydrocarbon backbone is investigated. Fundamental work is being performed to study the graft distribution, selectivity and mechanism by which this reaction occurs. A more thorough understanding of how this reaction proceeds will allow for the development of a more efficient industrial process.

Improvement of the efficiency of carbon dioxide (CO2) separation from flue gases has been identified as a high-priority research area to reduce the total energy cost of carbon capture and sequestration technologies in coal-fired power plants. Efficient CO2 removal from flue gases by adsorption systems requires the design of novel sorbents capable of capturing, concentrating and recovering CO2 on a cost-effective basis. The preparation of a novel aminosilane-functionalized cellulosic polymer sorbent by grafting of aminosilanes showed promising performance for CO2 separation and capture. A strategy for the introduction of N-(2-aminoethyl)-3-aminoisobutyldimethylmethoxysilane functionalities into cellulose acetate backbone by anhydrous grafting is described in this study. The dry sorption capacity of the aminosilane-functionalized cellulosic polymer reached 27 cc (STP) CO2/ cc sorbent at 1 atm and 39 cc (STP) CO2/ cc sorbent at 5 atm and 308 K. Exposure to water vapor slightly increased the sorption capacity of the sorbent, suggesting its potential for rapid cyclic adsorption processes under humid feed conditions. In addition, a strategy for the preparation of a cellulose acetate-titanium(IV) oxide sorbent by the reaction of cellulose acetate with titanium tetrachloride is presented. The organic-metal hybrid sorbent presented a sorption capacity of 14 cc (STP) CO2/ cc sorbent at 1 atm and 49 cc (STP) CO2/ cc sorbent at 5 atm and 308 K. The novel CO2 sorbents were characterized in terms of chemical composition, density changes, molecular structure, thermal stability, and surface morphology.