Water and ion transport critically determine the performance of many functional materials and devices, from fuel cells to lithium ion batteries to soft mechanical actuators. This dissertation aims to address some fundamental issues regarding transport and anisotropy, structural heterogeneity and molecular interactions inside ionic polymers. I first discuss a main deficiency of a standard protocol for calibrating high pulsed-field-gradient NMR. I show that high gradient calibration using low γ nuclei is not amenable to measurements on slow diffusing high γ nuclei. Then I employ NMR diffusometry to investigate transport and anisotropy for a series of ionic polymers, from poly(arylene ether sulfone) hydrophilic-hydrophobic multi-block copolymers to polymer blends to perfluorosulfonate random copolymers. For the multi-block copolymers, NMR diffusion measurements yield diffusion anisotropy as a function of water uptake and block lengths. ²H NMR spectroscopy on absorbed D₂O probes membrane alignment modes. These measurements also provide insights into average defect distributions. For the blend membranes, we examine the impact of compatibilizer on their transport properties. An increase in compatibilizer significantly improves the membrane phase homogeneity confirmed by SEM and transport studies. Theories of diffusion in porous media yield changes in domain size and tortuosity that correspond to drastic changes in local restrictions to water diffusion among different blend membranes. NMR relaxometry studies yield multi-component T₁ values, which further probe structural heterogeneities on smaller scales than diffusion experiments. For the random copolymer, the exploration of ion transport reveals inter-ionic associations of ionic liquids (ILs) modulated by hydration level and ionic medium. When ILs diffuse inside ionic polymers, isolated anions diffuse faster (≥ 4X) than cations at high hydration whereas ion associations result in substantially faster cation diffusion (≤ 3X) at low hydration inside membranes, revealing prevalent anionic aggregates. Finally, I present the strategy and analytical protocol for studying ionomer membranes using ILs. The normal cation diffusion contrasts to the anomalous anion diffusion caused by local confinement structures inside the membranes, which vary drastically with temperature and hydration level. These structures correspond to a density variation of SO₃⁻ groups, which define a distribution of local electrical potentials that fluctuate with temperature and nature of ionic media. / Ph. D.

This cumulative dissertation is a compilation of eight peer-reviewed, published scientific papers on the subject of two microscopic techniques of diffusion measurement, namely infrared (IR) microimaging and pulsed field gradient (PFG) NMR. The dissertation contains mainly five chapters. The first chapter introduces diffusion phenomena in general and concisely explains the importance and the current challenges of the investigation of molecular diffusion in nanoporous materials, which are the primary motivations behind the present work. To rise the challenges, it proposes an option of employing IR microimaging in parallel with PFG NMR in the measurement of the molecular diffusion. The second chapter describes the basic principles of the two diffusion measurement techniques and what they are capable of. Chapters 3 and 4 deliver convincing demonstrations of their applicability and potential in diffusion studies. Lastly, Chapter 5 concludes the present work by discussing complementary benefits of the two techniques, along with the novel application of the two-region model for assessing mass transfer in hierarchically porous materials.:Table of Contents CHAPTER 1. Introduction CHAPTER 2. Basics of diffusion measurement techniques 2.1. Introduction to infrared microscopy (IRM) 2.1.1. Working principle 2.1.2. Experimental setup 2.2. Introduction to pulsed field gradient nuclear magnetic resonance (PFG NMR) 2.2.1. Self-diffusion and propagator 2.2.2. Theory of PFG NMR CHAPTER 3. Applicability and potential of IRM • Publication 3.1. Anomaly in the chain length dependence of n-alkane diffusion in ZIF 4 metal-organic frameworks • Publication 3.2. Metal-organic framework Co-MOF-74-based host-guest composites for resistive gas sensing • Publication 3.3. Revealing the transient concentration of CO2 in a mixed-matrix membrane by IR microimaging and molecular modeling • Publication 3.4. IR microimaging of direction-dependent uptake in MFI-type crystals CHAPTER 4. Importance of PFG NMR in diffusion studies • Publication 4.1. NMR diffusometry with guest molecules in nanoporous materials • Publication 4.2. Structural characterisation of hierarchically porous silica monolith by NMR cryo-porometry and -diffusometry CHAPTER 5. Complementary benefits of IR microimaging and PFG NMR • Publication 5.1. Diffusion in nanopores: correlating experimental findings with 'first-principles' predictions • Publication 5.2. Diffusion analysis in pore hierarchies by the two-region model Bibliography Appendix A. Supporting information Appendix B. Author contributions

Pulsed field gradient (PFG) 1H NMR was used to characterize the mobility of ionic liquid cations in porous gas diffusion electrode (GDE) frameworks for metal–air electrochemical systems. The carbon GDE frameworks were produced by electrospinning. It was found that the motion of ionic liquids in the highly porous hosts is more complex than what is commonly exhibited by conventional fluids, which makes a multimodal investigation essential for an adequate description of mobility and wetting of GDEs. Observed NMR diffraction-like patterns cannot be linked to the tortuosity limit but may serve as a proxy for structural features in the fibrous material. While the observed data were interpreted using standard theoretical models, alternative explanations and causes for artifacts are discussed.

The first part of this dissertation (Chapters 1 to 4) describes the use of magnetic resonance techniques for polymeric material characterizations in solutions, with emphasis on methods utilizing magnetic field gradients - magnetic resonance imaging (MRI) and pulsed-field-gradient (PFG) NMR. The second part (Chapter 5) presents enhancements to dynamic nuclear polarization, an intensity enhancement approach for magnetic resonance techniques. In Chapter 2, I illustrate a characterization method to quantify free polymer chain content in a polymer/DNA complex (polyplex) formulation via one-dimensional proton NMR experiments. This assessment of free polymer quantity has critical impacts on in vivo gene transfection efficiency, cellular uptake, as well as toxicity of polycationic gene delivery vectors. Specifically, I investigated the complexation properties of three different polymeric "theranostic" agents, which combine an imaging functionality on the polymer as well as a DNA/RNA complexation component. These agents are under development to allow real time clinical monitoring of drug delivery and efficacy using MRI. Our NMR method provides simple and quantitative assessment of free and DNA-complexed polymers, including the actual polymer amine to DNA phosphate molar ratio (N/P ratio) within polyplexes. The NMR results are in close agreement with the stoichiometric number of polymer/DNA binding obtained by isothermal titration calorimetry. The noninvasive nature of this method allows broad application to a range of polyelectrolyte coacervates, for understanding and optimizing polyelectrolyte complex formation. Chapter 3 demonstrates a time-resolved MRI approach for measuring diffusion of drug-delivery polymeric nanoparticles on mm to cm scales as well as monitoring nanoparticle concentration distribution in bulk biological hydrogels. Our results show that as the particle size and surface charge become larger, collagen gel at tumor relevant concentration (1.0 wt.%) presents a more significant impediment to the diffusive transport of negatively charged nanoparticles. These results agree well with those obtained by fluorescence spectroscopies (neutral or slightly positively charged diffusing particles) as well as the proposed electrostatic bandpass theory of tumor interstitium (negatively charged particles). This study provides fundamental information for the design of polymeric theranostic vectors and carries implications that would benefit the understanding of nanoparticle transport in solid tumors. Furthermore, this work takes a significant step toward developing quantitative and real time in vivo monitoring of clinical drug delivery using MRI. Chapter 4 addresses the application of PFG-NMR for the determination of weight-average molar mass (Mw) for polyanions that have anti-HIV activity through the measurement of polymer diffusion coefficients in solutions. The effective characterization of molecular weights of polyelectrolytes has been a general and growing problem for the polymer industry, with no clear solutions in sight. In this study, we obtained the molar masses (Mw) for two series of sulfonated copolymers using sodium polystyrene sulfonate samples as molecular weight standards. PFG-NMR has notable advantages over conventional techniques for the characterization of charged polymers and shows great promise for becoming an effective alternative to chromatography methods. Chapter 5 is devoted to experimental and theoretical studies of liquid state dynamic nuclear polarization (DNP) via the Overhauser effect. Based on the adventurous work done by previous Dorn group members, we show that for 1H-nuclide-containing systems, the dipolar DNP enhancement can be significantly improved by decreasing the correlation time of the interaction by utilizing a supercritical fluid (SF CO2) which allows for greater dipolar enhancements at higher magnetic fields. For molecules containing the ubiquitous 13C nuclide, we show that previously unreported sp hybridized (H-C) alkyne systems represented by the phenylacetylene-nitroxide system exhibit very large scalar-dominated enhancements. Furthermore, we show for a wide range of molecular systems that the Fermi contact interaction can be computationally predicted via electron-nuclear hyperfine coupling and correlated with experimental 13C DNP enhancements. For biomedical applications, the enhancement of metabolites in SF CO2 followed by rapid dissolution in water or biological fluids is an attractive approach for future hyperpolarized NMR and MRI applications. Moreover, with the aid of density functional theory calculations, solution state DNP provides a unique approach for studying intermolecular weak bonding interaction of solutes in normal liquids and SF fluids. / Ph. D.

L’optimisation des performances d’une pile à combustible (PEMFC) requiert la compréhension microscopique des mécanismes de transport de l’eau et du proton confinés au sein de la membrane électrolyte polymère. La membrane est un matériau nanostructuré chargé, caractérisé par une dynamique de l’eau et du proton complexe et multi-échelle étroitement corrélée à la morphologie confinante. Nous nous sommes intéressés à la relation structure – transport dans i) L’Aquivion, un ionomère perfluorosulfonique récent présentant de bonnes performances en pile, ii) des systèmes «modèles» auto-assemblés de tensioactifs perfluorés formant des phases lamellaires et hexagonales et iii) une nouvelle membrane hybride préparée par dopage en tensioactif. La nano-structuration des différents systèmes a été étudiée par diffusion de rayonnement (X et neutrons), pour caractériser l’évolution de la structure (géométrie de la matrice hôte, taille de confinement) avec l’hydratation. Ensuite, nous avons sondé la dynamique de l’eau à l’échelle moléculaire (de la picoseconde à la nanoseconde) par diffusion quasi-élastique des neutrons (QENS) et à l’échelle micrométrique par RMN à gradients de champs pulsés. La comparaison membranes commerciales / systèmes modèles permet de discuter l’impact de la connectivité, du confinement et de la géométrie sur le transport ionique. Enfin, des membranes hybrides à fort potentiel ont été obtenues par dopage du Nafion et de l’Aquivion avec des tensioactifs. Ces nouveaux matériaux ouvrent une voie prometteuse pour la préparation de membranes polymères fortement anisotropes avec des chemins de conduction préférentiellement orientés. / The optimization of the Fuel Cell’s performances (PEMFC) requires a microscopic understanding of the water and proton’s transport mechanism, which are confined in a polymer electrolyte membrane. The latter is nanostructured, charged and characterized by a complex and multi-scale water and proton dynamics, closely correlated to the confining morphology. We studied the structure-transport interplay in i) the Aquivion, a recent perfluorosulfonic ionomer exhibiting good performances in fuel cell, ii) “model” systems of perfluorosulfonic surfactants, which self-assemble in lamellar and hexagonal phases and iii) a new hybrid membrane doped with surfactant. The nanostructuration of the different systems has been studied by neutron and X-ray scattering, to characterize the structural evolution (host matrix geometry, confinement sizes) with hydration. Then, we probe the water dynamics at the molecular level (from picosecond to nanosecond) with Quasi-Elastic Neutron Scattering (QENS) and at the micrometric scale with Pulsed Field Gradient NMR. The comparison of commercial membranes and model systems bring new insight on the impact of the connectivity, the confinement and the geometry, on the ionic transport. Finally, high potential hybrid membranes have been obtained by doping Nafion and Aquivion with surfactants. Those new materials open a promising way for the preparation of highly anisotropic polymer membrane, with conducting path preferentially oriented.