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Nuclear magnetic resonance (NMR) provides a variety of tools for the structural characterization of porous solids. In this paper, we discuss a relatively novel approach called NMR cryodiffusometry, which is based on a simultaneous assessment of both the phase state of intraporous liquids at low temperatures, using NMR cryoporometry, and their transport properties, using NMR diffusometry. Choosing two model porous materials with ordered and disordered pore structures as the host systems, we discuss the methodological and fundamental aspects of the method. Thus, with the use of an intentionally micro-structured mesoporous silicon, we demonstrate how its structural features give rise to specific patterns in the effective molecular diffusivities measured upon progressive melting of a frozen liquid in the mesopores. We then present the results of a detailed study of the transport properties of the same liquid during both melting and freezing processes in Vycor porous glass, a material with a random pore structure. 1

<p>In this thesis we present a ⁷⁷Se NMR study of the iron selenide based high-temperature superconductor K_xFe_2−ySe₂ (T_c = 33 K). We observe NMR lineshapes as narrow as ∼ 4.5 kHz with an applied field along the crystal c-axis, and find no evidence for the co-existence of magnetic order with superconductivity. With an applied field along the ab plane, however, the lineshape splits into two peaks of equal intensities at all temperatures, suggesting that the tetragonal fourfold symmetry of the average structure may be locally lowered by vacancy superstructure. Knight shift data indicate that spin susceptibility decreases progressively with temperature, similar to other iron arsenide high-T_c systems. In the nuclear spin-lattice relaxation rate 1/T₁ we observe no Hebel-Slichter coherence peak, nor any enhancement in low frequency antiferromagnetic spin fluctuations in 1/T₁T. We also report on the effects of sulphur (S) substitution on the selenium sites in this system by conducting ⁷⁷Se NMR measurements on K_xFe_2−ySe_2−zS_z (z = 0.8, 1.6). We find that both spin susceptibility and low frequency spin fluctuations are suppressed with increasing S content along with T_c.</p> / Master of Science (MSc)

This thesis presents analyses of hydrogen-bonded materials using solid-state nuclear magnetic resonance (NMR) spectroscopy. Proton dynamics were investigated in two classes of phosphate-based proton conductors: phosphate solid acids and tin pyrophosphates. These materials have the potential to be used as solid state proton conductors in fuel cells. Proton dynamics in phosphate solid acids were probed based on the attenuation of homonuclear dipolar coupling with increasing temperature. These studies showed that homonuclear dipolar recoupling NMR techniques can be employed in complex multi-spin systems. Additionally, two pathways for proton hopping in monoclinic RbH2PO4, a sample with two proton environments, were identified and quantified for the first time using a combination of dipolar recoupling and proton exchange NMR methods. Tin pyrophosphates, another class of solid-state proton conductor with analogous phosphate tetrahedral structure, were studied. Proton dynamics had to be analyzed via exchange-based NMR techniques as a result of low proton concentration in these materials. Proton mobility in tin pyrophosphate was found to increase with increased protonation. Furthermore, hydrogen bonding was investigated as a coordination mode in silicone boronic acid (SiBA) elastomers, potential materials for contact lens manufacture. As in the phosphate-based proton conductors, hydrogen bonding played an important role in the structure of the SiBA elastomers as one of the mechanisms through which these materials crosslink. In addition to hydrogen bonding, covalent bonding between boronic acids was found to occur at three- and four-coordinate boron centers. The purpose of this study was to determine the influence of boronic acid loading and packing density on crosslinking in SiBA elastomers. Boron coordination environments were investigated by 11B quadrupolar lineshape analysis. The incidence of four-coordinate dative bonding, a predictor of the stress-strain response in these materials, increased with boronic acid loading but was most heavily influenced by boronic acid packing density. / Thesis / Doctor of Philosophy (PhD) / Hydrogen bonds are intermolecular interactions that are significant in many structural (low crystal density in ice) and dynamic (enzymatic processes occurring under biological conditions) processes that are necessary to maintain life. In this thesis, solid-state nuclear magnetic resonance (NMR) spectroscopy is used to explore proton dynamics of hydrogen-bonded networks in various materials. Advanced NMR experiments that probe homo- and heteronuclear dipolar coupling interactions revealed possible pathways for proton transport in phosphate-based proton conducting materials. This study provided a better understanding of ion conducting mechanisms that can be used in intermediate-temperature fuel cell applications. Additionally, solid-state NMR was used in the identification of hydrogen bonding and other coordination modes in silicone boronate acids (SiBA), a class of elastomers with potential applications as contact lens. Boron coordination in SiBA elastomers was dependent on both boronic acid loading and boronic acid packing density.

Batteries play a pivotal role in the modern world, powering everything from portable electronics to electric vehicles, and are critical in the shift towards renewable energy sources by enabling efficient energy storage. This thesis presents new computational strategies to understand and predict surface degradation and stacking faults in battery cathodes, phenomena that have crucial impact on the battery lifetime. The starting point is a detailed first-principles analysis of LiNiO₂ surface degradation, assessing the thermodynamics of oxygen release and its impact on the surface integrity of this prospective cathode material. This research led to the development of a method for the automated enumeration of surface reconstructions and the development of a Python software package implementing the methodology, thereby greatly accelerating the computational surface characterization of electrode materials. The methodology made it feasible to extend the investigation to LiCoO₂ surfaces, comparing their oxygen retention and surface stability with LiNiO₂ and identifying the unique properties of the two transition metals that control their behavior during battery operation. In addition to surface phase changes, stacking faults are another important class of two-dimensional defects that can affect the properties of cathode materials. Combining information from first principles calculations with 17O nuclear magnetic resonance (NMR) spectroscopy provided by collaborators, we uncovered how stacking faults affect the capacity and cyclability of Li₂MnO₃ cathodes, a prototypical lithium-rich material with oxygen redox activity. Although automated first-principles calculations are, in principle, an ideal tool for understanding atomic-scale degradation phenomena in batteries, they are computationally demanding and, therefore, limited to materials with simple compositions. In the final chapter, we explore the application of machine learning for further accelerating computational battery degradation simulations by leveraging existing data first-principles calculations for predicting the stability of new surface reconstructions. This chapter points toward a new direction that should be further explored in the future. The research presented in this thesis not only advances the understanding of lithium-ion battery cathode materials but also introduces more-widely applicable computational methodologies that lay a foundation for the development of advanced materials for energy storage applications. This work demonstrates the benefits of integrating traditional computational methods with machine learning, contributing to ongoing progress in materials science and opening up new possibilities for advancements in energy technology and material engineering.

The performance of polymeric diphenylmethane diisocyanate (PMDI) resin is known to be highly dependent on the wood species. This species dependence may be due to differences in: cure chemistry, interphase morphology, or both of these factors. This study addresses aspects of the cure chemistry and interphase morphology of wood/PMDI bondlines; specifically these effects are compared using two woods: yellow-poplar and southern pine. In this study, the cure chemistry of wood-PMDI system was analyzed with solid state NMR (SSNMR) using wood samples cured with doubly labeled (15N,13C) PMDI resin. The kinetics of PMDI cure in the presence of wood was analyzed with differential scanning calorimetry. Thermogravimetric analysis was used to analyze the effect of resin impregnation on the degradation patterns of wood. The wood-PMDI bond morphology was probed with dynamic and static (creep) mechanical analyses in both dry and plasticized conditions. The effect of resin on wood polymer relaxations was quantitatively analyzed by both the time-temperature superposition principle and the Kohlrausch-Williams-Watts equation. The presence of a small but statistically significant species effect was observed on both the cure chemistry and bond morphology of wood-PMDI system at low cure temperatures. The cure of PMDI resin was found to be significantly faster in pine relative to corresponding poplar samples. Resin impregnation showed a significant species dependent effect on the wood mechanical properties; the resinated pine samples showed increase in compliance while the corresponding poplar samples became stiffer. The in situ lignin relaxation was studied with both dynamic and static modes, using plasticized wood samples. Results showed that the lignin relaxation was slightly affected by resin impregnation in both woods, but the effect was relatively larger in pine. Static experiments of dry wood samples showed a significant reduction in the interchain interactions of wood polymers in pine samples, exclusively. Investigation of plasticized pine samples, which focuses on the in situ lignin relaxations, showed only minor changes with resin impregnation. This led us to hypothesize that the large changes observed in dry samples, were due to the in situ amorphous polysaccharides. The wood-PMDI interactions were significantly reduced upon acetylation of wood. This study also discusses three new and highly sensitive methods for the analysis of wood-resin interactions. / Ph. D.

Disabled-2 (Dab2) is an adapter protein that interacts with cell membranes and it is involved in several biological processes including endocytosis and platelet aggregation. During endocytosis, the Dab2 phosphotyrosine-binding (PTB) domain mediates protein binding to phosphatidylinositol 4,5-bisphosphate (PIP2) at the inner leaflet of the plasma membrane and helps co-localization with clathrin coats. Dab2, released from platelet alpha granules, inhibits platelet aggregation by binding to the °IIb? integrin receptor on the platelet surface through an Arg-Gly-Asp (RGD) motif located within the PTB domain. Alternatively, Dab2 binds sulfatides on the platelets surface, and this binding partition Dab2 in two pools (sulfatide and integrin receptor-bound states), but the biological consequences of lipid binding remain unclear. Dab2 binds sulfatides through two basic motifs located on its N-terminal region including the PTB domain (N-PTB). We have characterized the binding of Dab2 to micelles, which are widely used to mimic biological membranes. These micellar interactions were studied in the absence and presence of Dab2 lipid ligands, sulfatides and PIP2. By applying multiple biochemical, biophysical, and structural techniques, we found that whereas Dab2 N-PTB binding to PIP2 stabilized the protein but did not contribute to the penetration of the protein into micelles, sulfatides induced conformational changes and facilitated penetration of Dab2 N-PTB into micelles. This is in agreement with previous observation that sulfatides, but not PIP2, protect Dab2 N-PTB from thrombin cleavage. By studying the mechanism by which Dab2 targets membranes, we will have the opportunity to manipulate its function in different lipid-dependent biological processes. / Master of Science

Adaptor proteins, like Tollip and Tom1, facilitate cellular cargo sorting through their ubiquitin-binding domains. Tollip and Tom1 bind to each other through their TBD and GAT domains, respectively, whereas Tollip interacts with phosphatidylinositol-3-phosphate (PtdIns(3)P)-containing endosomal membranes. Tom1 and Tollip interaction and association with endosomes is proposed to be involved in the lysosomal degradation of polyubiquitinated cargo. Through cellular, biochemical, and biophysical techniques, we have further characterized the association of Tom1 with Tollip. Mutations in the binding interface of the Tom1 GAT and Tollip TBD complex leads to a subcellular mis-localization of both proteins, indicating that Tom1 may serve to direct Tollip to specific cellular pathways. It was determined that Tom1 inhibits the binding of Tollip to PtdIns(3)P and inhibition was reversed when mutations in the binding interface of the Tom1 GAT and Tollip TBD were present. Furthermore, it was established that, upon the binding of Tollip TBD to Tom1 GAT, ubiquitin is inhibited from binding to Tom1 GAT. It was also demonstrated that Tom1 GAT, but not Tollip TBD, can weakly bind to PtdIns(3)P. Consequently, we propose that association of Tom1 may serve to direct Tollip for involvement in specific cell signaling pathways. Gaining insight into the function of Tom1 and Tollip may lead to their use as therapeutic targets for increasing the efficiency of cargo trafficking and also for patients recovering from various cardiac injuries. / Master of Science

The N-heterocyclic carbene (NHCs) based pincer ligands field is still in its infancy after decades. They are known for their applications in organocatalysis, coordinating with transition metals and p-block elements, catalysis, and material chemistry. Among all NHCs, CCC-NHC-based on late-transition metal complexes were first developed by our group in 2005 with a unique metalation/transmetalation strategy. Our group also designed the chiral version of these CCC-NHC ligands to synthesize its metal complexes. However, their asymmetric catalytic applications were unknown. Wanting to expand on this work, we first successfully synthesized achiral CCC-NHC pincer complexes and their new catalytic application, as it is economically cheaper than directly working on developing a chiral version for catalysis. Then, different chiral CCC-NHC salts were synthesized based on different chiral arms and N-substituents on NHCs to modify their steric hindrance and electronic structure properties. These precursors were used for their enantioselective application in nucleophilic catalysis. In Chapter II, we will discuss the synthesis of the CCC-NHC pincer Ir (III) dimer complex and its first catalytic application in C−H functionalization of N-methylindoles with alpha-aryl-alpha-diazoacetates at the C-3. The best reaction conditions involve a combination of catalysts and substrates in a specific order. It resulted in the activation of the C-H bond with the formation of a new C-C bond to generate alpha-aryl-alpha-indolyl acetates with more than 99% conversion at room temperature without requiring any additives. The substrate scope and limitations of N-methyl indoles and diazoacetates were also explored. Chapter III will focus on a new modified synthetic route to synthesize and characterize chiral CCC-NHC chloride salts in a shorter synthetic route than the known one. The metalation/transmetalation of chiral CCC-NHC ligands with late transition metals and the initial attempt in asymmetric catalysis will be discussed in Chapter IV. Chapter, V, demonstrated nucleophilic catalysis of CCC-NHC precursors in benzoin condensation of aldehyde. The study started with the evaluation of fifteen different achiral bis-CCC-NHC salts based on triazole, imidazole, and benzimidazole. Further studies with chiral CCC-NHC salts also resulted in more than 99% conversion and 99% ee in benzoin products. The substrate scope of benzaldehyde with different substituents was also explored