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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.

For the first time nonwoven fibrous scaffolds were electrospun from a low molar mass gemini ammonium surfactant, N,N–-didodecyl-N,N,N–,N–-tetramethyl-N,N–-ethanediyl-di-ammonium dibromide (12-2-12). Cryogenic transmission electron microscopy (cryo-TEM) and solution rheological experiments revealed micellar morphological transitions of 12-2-12 in water and water:methanol (1:1 vol). Electrospinning efforts of 12-2-12 from water did not produce fibers at any concentration, however, electrospinning 12-2-12 in water:methanol at concentrations greater than 2C* produced, hydrophilic continuous fibers with diameters between 0.9 and 7 μM. Photo-reactive surfactants were synthesized to electrospin robust surfactant membranes. Before electrospinning it was important to fundamentally understand the structure-property relationship of gemini surfactants. The thermal and solution properties were explored for a series of ammonium gemini surfactants using differential scanning calorimetry (DSC), polarized light microscopy (PLM), and conductivity experiments. The Kraft temperature (Tk) was measured in water and water:methanol (1:1 vol) to investigate the influence of solvent on the surfactant solution properties. Other experiments investigate how associated photo-curable architectures are applicable in macromolecular architectures, to gain a fundamental understanding of how hydrogen bonding associations influence the photo-reactivity of functionalized acrylic copolymers. Novel hot melt pressure sensitive adhesives (HMPSAs) were developed from acrylic terpolymers of 2-ethylhexyl acrylate (EHA), 2-hydroxyethyl acrylate (HEA), and methyl acrylate (MA) functionalized with hydrogen bonding and photo-reactive functionalities. The synergy of hydrogen bonding and photo-reactivity resulted in higher peel values and rates of cinnamate photo-reactivity with increasing urethane concentration. Random copolymers of poly(n-butyl acrylate (nBA)-co-2-hydroxyethyl methacrylate (HEMA)) were functionalized with hydrogen bonding and photo-reactive groups to explore the photo-curing of associated macromolecular architectures. The influence of urethane hydrogen bonding on the photo-reactivity of cinnamate-functionalized acrylics was investigated with photo-rheology and UV-vis spectroscopy. Cinnamate-functionalized samples displayed an increase in modulus with exposure time, and the percentage increase in modulus decreased as the urethane content increased. The synergy of hydrogen bonding and photo-reactive groups resulted in higher rates of cinnamate photo-reactivity with increasing urethane concentration. Electrospun fibers were in situ photo-crosslinked to develop fibrous membranes from cinnamate functionalized low Tg acrylics. Electrospinning was conducted approximately 55 °C above the Tg of the cinnamate acrylate and the electrospun fibers did not retain their fibrous morphology without photo-curing. However, electrospun fibers were collected that retained their fibrous morphology and resisted flow when in situ photo-cured during electrospinning. The intermolecular photo-dimerization of cinnamates resulted in a network formation that prevented the low Tg cinnamate acrylate from flowing. / Ph. D.

Phosphorus-containing high performance polymers have been extensively studied during the last 10 years. These materials are of interest for a variety of optical and fire resistant properties, as well as for their ability to complex with the inorganic salts. This dissertation has focused on the nature of the phosphonyl group interactions with hydroxyl containing polymers, such as the poly(hydroxy ether)s. These may be considered linear models of epoxy resins and are also closely related to dimethacrylate (vinyl ester) matrix resins that are important for composite systems. It has been shown that bisphenol A poly(arylene ether phosphine oxide/sulfone) homo- or statistical copolymers are miscible with a bisphenol A-epichlorohydrin based poly(hydroxy ethers) (PHE), as shown by dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC), infrared spectroscopy and , solid state cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS). These measurements illustrate the strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the PHE as the miscibility inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mole% of phosphine oxide units in the poly(arylene ether) copolymer. Replacement of the bisphenol A moiety by other diphenols, such as hydroquinone, hexafluorobisphenol A and biphenol did not significantly affect blend miscibilities. Miscible polymer blends with PHE were also made by blending poly(arylene thioether phosphine oxide), and fully cyclized phosphine oxide containing polyimides based on (prepared from 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) and bis(m-aminophenyl) methyl phosphine oxide (DAMPO)) or bis(m-aminophenyl) phenyl phosphine oxide). Additional research has focused on the influence of these materials on the property characteristics of vinyl ester matrix resins and has shown that the concentration of phosphonyl groups controls the homogeneity of both oligomers and the resulting networks. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fracture toughness measurements further confirmed the qualitative observations. Metal salts, such as CoCl2 and CuCl2 had earlier been demonstrated to form complexes/nanocomposites with phosphorus-containing poly(arylene ethers). It has been possible to prepare transparent films with 100 mol% of metal chlorides, based upon the phosphonyl groups. The films are transparent, unlike the opaque polysulfone control systems. FTIR results suggested the formation of inorganic salt and polymer complexes at low concentrations. TEM showed homogeneous morphology at low concentrations and excellent dispersion even at high mole % of salts. Cobalt materials reinforce the basic poly(arylene ether)s to provide higher modulus values and influence positively the char yield generated after TGA experiments in air. The cobalt salt/BPADA-DAMPO polyimide composites also yield transparent films, implying very small dimensions. Silica-polymer nanocomposites were also produced by mixing commercial silica colloid/N,N-dimethylacetamide (DMAc) fine dispersions (~ 12 nm) with bisphenol A poly(arylene ether phenyl phosphine oxide). The dry films produced by solution casting are transparent and silica colloids are evenly dispersed (~ 12 nm) into the polymer matrix as shown by TEM. These nanocomposites increased char yield compared with the polymer control, suggesting their fire retardant character. In comparison, the silica/polysulfone hybrid films prepared by the same methods were opaque and the char yield was not improved. This different phase behavior has been explained to be due to the hydrogen bonding between phosphonyl groups and silanol hydroxyl groups on the surface of the nanosilica. / Ph. D.

The ring opening polymerization of D,L-lactide (DLLA) using multifunctional hydroxyl-terminated initiators and catalyst/coinitiator systems based on Sn(Oct)2 afforded the preparation of star-shaped, poly(D,L-lactide)s (PDLLA)s of controlled molar mass, narrow molar mass distributions, and well-defined chain end functionality. Various modifications of star-shaped PDLLA resulted in macromolecules with tailored functionalities for biomedical applications. Star-shaped PDLLAs were modified to contain photoreactive methacrylate end groups and subsequent photo-crosslinking was performed. Photo-crosslinked networks based on methacrylated star-shaped PDLLAs exhibited thermal properties and mechanical performance that were superior to current approved clinical adhesives. In addition, the thermal and mechanical properties of the networks were strongly dependent on the composition and molar mass of the star-shaped PDLLA precursors. Tensile strengths in the range of 8-21 MPa were obtained while the Young's modulus increased from 12 to 354 MPa and were higher for networks based on urethane containing polymers. Star-shaped PDLLAs bearing complementary adenine and thymine terminal units were also prepared. The hydrogen bonding associations between complementary PDLLA macromolecules depended strongly on molar mass and hence, the concentration of multiple hydrogen bonding units. 1H NMR spectroscopy confirmed the formation of hydrogen-bonded complexes with a 1:1 optimal stoichiometry and an association constant of 84 M-1. The hydrogen-bonded complexes also exhibited significantly higher solution viscosities than non-blended polymer solutions of similar molar mass and concentration. Thermoreversible associations of PDLLA-based complementary polymers were observed in the melt phase and the melt viscosity of a blended complex was consistently an order of magnitude higher than non-functionalized star-shaped PDLLA of similar molar mass. Furthermore, melt electrospinning of the hydrogen-bonded complexes successfully resulted in fibers of significantly larger diameter (9.8 ± 2.0 µm) compared to the individual precursors (PDLLA-A = 4.0 ± 0.6 µm and PDLLA-T = 4.4 ± 1.0 µm). These results suggested that thermoreversibility, as well as the strength of the hydrogen bonding interactions between the end groups of the tailored star-shaped PDLLA-based supramolecular polymers controlled the fiber diameter in the melt electrospinning process. Highly ordered microporous honeycomb structures were developed on photo-functional star-shaped PDLLA surfaces. The pore dimensions were dependent on polymer solution concentration, polymer molar mass and relative humidity. The combination of self-organizing and cross-linking techniques resulted in free-standing, PDLLA membranes with high chemical stability as well as higher mechanical strength for further material patterning. Amikacin, an antibiotic commonly used for treating infections was successfully encapsulated in star-shaped PDLLA fibers that were electrospun from solution. Preliminary results suggested that molecular architecture influenced the encapsulation of the antibiotic and subsequent drug release profile. / Ph. D.

The nitrate radical (NO3·) was first identified as early as the 1881, but its role in atmospheric oxidation has only been identified within recent decades. Due to its high one-electron reduction potential and its reactivity toward a diverse set of substrates, it dominates nighttime atmospheric oxidation and has since been the subject of much work. Despite this, studies on NO3· hydrogen atom transfer reactions have been somewhat neglected in favor of its more reactive oxidative pathways. The first section of the dissertation will highlight the role of substrate structure, solvent effects, and the presence of a polar transition state on NO3· hydrogen abstractions from alcohols, alkanes, and ethers. In this work the acquisition of absolute rate constants from previously unexamined substrates was analyzed alongside a curated list of common organic pollutants degraded through hydrogen atom abstraction. It was found that NO3· reacts with low selectivity through an early polarized transition state with a modest degree of charge transfer. Compared to the gas-phase, condensed-phase reactions experience rate enhancement—consistent with Kirkwood theory—as a result of the polarized transition state. These insights are then applied to abstractions by NO3· from carboxylic acids in the next section. It was found that the rate constants for abstraction of α-carbons were diminished through induction by the adjacent carbonyl compared to the activation seen for the aforementioned substrates. The deactivation of abstraction by the carbonyl was found to be dramatically reduced as the substrate's alkyl chain was lengthened and/or branched. This apparent change in mechanism coincides with hydrogen abstraction of the alkyl chain for sufficiently large carboxylic acids and rules out the possibility of concerted bond breaking elsewhere in the molecule. Finally, the dissertation will cover some additional projects related to the overall nature of the work including examination of the kinetics of radical clock systems when complexed with metal ions and the examination of a highly oxidative biosourced monomer. / Doctor of Philosophy / The nitrate radical (NO3·) was first identified as early as the 1881, but its role in the breakdown of atmospheric pollutants has only been identified within recent decades. Operating primarily at night, NO3· serves as a major atmospheric oxidant—it breaks down pollutants by reactions that involve the removal of electrons from those substrates. This chemistry is particularly important in understanding the consequences of an increasingly industrialized world and the subsequent short-term health and environmental implications. Geographically, these reactions will occur in large concentrations near locations that contribute greatly to atmospheric pollution, such as above coal-powered plants, heavily industrialized areas, above the canopy of large forests, and immediately behind the engines of airplanes as they move through the sky. The proximity of these locations to large population centers has caused the pollutants to greatly impact human health. These contaminants have been linked to several of the leading global causes of death, such as ischemic heart disease, stroke, and respiratory illnesses. The first section of the dissertation will focus on the role of pollutant structure, the medium in which the reaction occurs, and the development of a charged complex when NO3· reacts with alcohols, alkanes, and ethers. These substrates are often found as the result of incomplete combustion when burning fuel or as products of even more sustainable biodiesels. In this work the exact rate constants were found for substrates that were previously unexamined and compared with similar known reaction rates. It was found that NO3· has a low preference for what it reacts with and passes through a modestly charged complex early in the reaction. Compared to gaseous reactions, reactions in a liquid environment proceed faster due to the formation of a charged complex. This was then applied to reactions with carboxylic acids in the next section. Carboxylic acids are often found in large concentrations above the canopy of large forests resulting from the oxidation of isoprenes that are naturally released from broad-leaf trees. It was found that these reactions were slower than reactions with alkanes as the development of the charged complex was inhibited due to the presence of an adjacent dipole. When the carboxylic acid was longer and/or more branched, the formation of the charged complex was no longer inhibited as the reaction site moved further from the dipole. A change in reaction pathway was observed when the acids were sufficiently large. This ruled out the possibility of the reaction occurring simultaneously with a fracturing and rearrangement elsewhere. Finally, the dissertation will cover some additional projects that share some overlap with the work already described including the study of the rates of radical clock systems in the presence of metal ions and the study of naturally sourced monomers that are prone to losing electrons.

The mechanism and the oxidation potential of the dissociative single electron transfer for tetra-n-butylammonium acetate has been investigated via conventional (cyclic voltammetry) and convolution voltammetry. The oxidation potential for tetra-n-butylammonium acetate was determined to be 0.60 ± 0.10 (vs. Ag/ (0.1 M) AgNO₃) in anhydrous acetonitrile. The results also indicated the mechanism of oxidation was concerted dissociative electron transfer (cDET), rather than stepwise as was previously reported. To further investigate the mechanism, a series of aliphatic and aromatic tetra-n butylammonium carboxylates were synthesized and investigated via convolution and conventional methods under anhydrous conditions (propionate, pivalate, phenyl acetate, and benzoate). The reported results showed high reproducibility and consistency with a concerted dissociative electron transfer for aliphatic carboxylates with a systematic shift in the oxidation potentials (0.60 ± 0.09 V for acetate, 0.47 ± 0.05 V for propionate, and 0.40 ± 0.05 V for pivalate) within the series which is expected trend based on radical stabilization energies of the alkyl groups on the aliphatic carboxylates. Hydrogen bonding was investigated as a possible source for the discrepancy between our results and the reported mechanism of the dissociative electron transfer. Because of the extreme hygroscopic nature of carboxylate salts, it was hypothesized that the presence of small amounts of water might alter the reaction mechanism. Deionized water and deuterium oxide additions to anhydrous acetonitrile were performed to test this hypothesis. The mechanism was noted to shift towards a stepwise mechanism as water was added. In addition, the derived oxidation potentials became more positive with increasing concentrations of water. Several explanations are presented with regards to water effects on the shift in the electron transfer mechanism. Indirect electrolysis (homogeneous redox catalysis) was also employed as an alternative and independent approach to quantify the oxidation potentials of carboxylates. A series of substituted ferrocenes were investigated as mediators for the oxidation of tetra-n-butylammonium acetate. Preliminary data showed redox catalysis was feasible for these systems. Further analyses of the electrochemical results suggested a follow-up chemical step (addition to mediator) that competes with the redox catalysis mechanism. As predicted from theoretical working curves, a plateau region in the i_p/i_pd plots (where no meaningful kinetic information could be obtained) was observed. Products mixture analyses verified the consumption of the mediator upon electrolysis, but no further information with regards to the nature of the mechanism was deduced. In a related study the effects of hydrogen bonding and ions on the reactivity of neutral free radicals were examined by laser flash photolysis. The rate of the β-scission of the cumyloxyl radical is influenced by cations (Li⁺ > Mg²⁺ ≈ Na⁺ > ⁿBu₄N⁺) due to stabilizing ion-dipole interactions in the transition state of the developing carbonyl group. Experimental findings are in a good agreement with theoretical work suggesting metal ion complexation can cause radical clocks to run fast with a more significant effect if there is an increase in dipole moment going from the reactant to the transition state. / Ph. D.

Master of Science

Segmented copolymers are a commercially important class of materials that are utilized in a wide variety of applications. In these systems a relatively large number of variables such as backbone chemistry, segment molecular weight, and the overall molecular weight of the copolymer can be independently controlled to engineer materials with targeted properties. Such versatility also means that a large number of variables can influence the morphology and therefore, properties and performance of segmented copolymers. In this dissertation, the influence of selected variables on the solid state structure-property behavior of segmented poly(ether-block-amide), polyurethane, polyurethaneurea, and polyurea copolymers is explored. The specific variables which have been utilized singly or in conjunction with others are hard segment crystallizability, crystallization conditions, hard segment content, soft segment type and molecular weight, nature of hydrogen bonding, extent of inter-segmental hydrogen bonding, segment symmetry, and chain architecture. In poly(ether-block-amide)s, it was found that the morphology of both the crystalline and the amorphous phase depend upon the polyamide content of the sample and, as expected, the crystallization conditions. A comparison of polydimethylsiloxane based segmented polyurethanes with their polyurea counterparts demonstrated that for a constant hard segment content the soft segment molecular weight particularly governs the extent of microphase separation in these materials. The nature of hydrogen bonding, monodentate or bidentate, also strongly influences their mechanical response. Remarkably, the polyurea sample with a polydimethylsiloxane molecular weight of 7000 g/mol and a hard segment content of 25 wt % exhibited a remarkable service temperature window (for rubber-like behavior) of ca. 230°C (from -55°C to 175°C) whereas it was ca. 200°C wide (from -55°C to 145°C) for the equivalent polyurethane sample. The extremely high chemical incompatibility between the polydimethylsiloxane of sufficiently high molecular weight and urethane or urea segment is expected to generate a relatively sharp interface between the soft matrix and the dispersed hard domains. Therefore, a polyether co-soft segment was incorporated in a controlled manner along the chain backbone, which resulted in inter-segmental hydrogen bonding between the ether and the urea segments. The consequent segmental mixing gave rise to a gradient interphase, which led to a significant improvement in the tensile strength, and elongation at break in selected polydimethylsiloxane segmented polyurea copolymers. The importance of the hydrogen bonding network in model polyurethaneurea copolymers was also explored by utilizing LiCl as molecular probe. It has been demonstrated that hydrogen bonding plays an important role, over and above microphase separation, in promoting the long-range connectivity of the hard segments and the percolation of the hard phase through the soft matrix. The incorporation of hard segment branching in these polyurethaneurea also reduced the ability of the hard segments to pack effectively and establish long-range connectivity. The disruption of the percolated hard phase resulted in a systematic softening of the copolymers. The role of chain architecture in governing the structure/property/processing of segmented was also investigated by comparing highly branched segmented polyurethaneureas with their linear analogs. These copolymers were based on poly(propylene oxide) or poly(tetramethylene oxide) as the soft segments The highly branched copolymers utilized in this dissertation were able to develop a microphase morphology similar to their linear analogs. Particularly noteworthy, and surprising, was the observation of weak second order interference shoulder in the respective small angle X-ray scattering profiles of the highly branched samples based on poly(propylene oxide) of MW 8200 and 12200, indicating the presence of at least some level of long-range order of the hard domains in these samples. Tapping-mode atomic force microscopy phase images of these two samples clearly confirmed the small angle X-ray scattering results. In addition to the strain induced crystallization of the poly(tetramethylene oxide) MW 2000 g/mol based linear polyurethaneureas, the highly branched analog of this sample also exhibited similar behavior at ambient temperature and uniaxial deformation of ca. 400 % strain. Wide angle X-ray scattering confirmed the above observation. The reduced ability of the branched polymers to entangle resulted in slightly poorer mechanical properties, such as tensile strength, elongation at break, and stress relaxation as compared to their linear analogs. However, primarily due to their reduced entanglement density, the branched polyurethaneureas had significantly lower ambient temperature solution viscosity as compared to their linear polyurethaneurea analogs. Therefore, these highly branched polyurethaneureas can be more easily processed than the latter materials. Finally, it was demonstrated that non-chain extended segmented polyurethane and polyurea copolymers in which the hard segment is based on only a single diisocyanate molecule may well exhibit properties, such as the breadth of the service window, the average plateau modulus, stiffness, tensile strength, and elongation at break that are similar to chain extended segmented copolymers that possess distinctly higher hard segment content. A careful control of the hard segment symmetry and the nature of the hydrogen bonding is necessary to achieve such improved performance in the non-chain extended systems. Therefore, the results of this study provide new direction for the production of thermoplastic segmented copolymers with useful structural properties. / Ph. D.

Yes / We describe the Δlog P method for the assessment of intramolecular hydrogen bonds (IMHBs), and show that it is not a very general method of distinguishing between molecules in which there is an IMHB and molecules in which there is no IMHB. The ‘double’ Δlog P method of Shalaeva et al. is a much more reliable method for the assessment of IMHB but requires the synthesis of a model compound and the determination of no less than four water-solvent partition coefficients. In addition, it is difficult to apply to compounds that contain more than one hydrogen bond acidic group capable of IMHB. We then describe our NMR method of assessing IMHB, based on 1H NMR chemical shifts in solvents DMSO and CDCl3. We have determined 1H NMR chemical shifts for a number of ortho-substituted anilines and show that the only compound we have studied that forms an IMHB is methyl 2-methylaminobenzoate though there is no IMHB present in methyl 2-aminobenzoate. This apparently anomalous result is supported by both MM and ab initio calculations. The NMR method is much simpler and less time consuming than other methods for the assessment of IMHB. It provides a quantitative assessment of IMHB and can be applied to molecules with more than one hydrogen bond acidic group.