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A NMR study of the structure-dynamics relationships in heterogeneous materials is presented. In the first part, transport in soft-matter systems is studied using the pulsed field gradient NMR technique (PFG NMR). The molecular crowding effect in biological matter has been addressed using polymer solutions as model systems. By performing ensemble-based diffusion studies, the earlier obtained data on anomalous diffusion have been complemented. The transition to normal diffusion on a larger time scale has been shown. Taking advantages of the NMR approach, transport properties of microemulsions consisting of micellar colloids dissolved in liquid crystals have been investigated. The self-diffusivities measured under equilibrium conditions have shown weak correlations with microscopic ordering and macroscopic phase transitions occurring in the systems under study. The formation of micelles is shown to be decisive for macroscopic separation at the isotropic-nematic transition. The second part of the thesis covers heterogeneous effects in diffusion for fluids in porous solids, as probed using a combination of NMR diffusometry and structure characterization methods. Ionic liquids have been investigated, revealing a complex behavior under confinement. The attempts to correlate the observed characteristics of the ionic liquids with their internal chemical structure were undertaken. Finally, the series of nanoporous glasses with tunable pore structure characteristics were studied. Strong correlations between their structure and the preparation conditions as well as between the resulting transport properties have been shown.

A NMR study of the structure-dynamics relationships in heterogeneous materials is presented. In the first part, transport in soft-matter systems is studied using the pulsed field gradient NMR technique (PFG NMR). The molecular crowding effect in biological matter has been addressed using polymer solutions as model systems. By performing ensemble-based diffusion studies, the earlier obtained data on anomalous diffusion have been complemented. The transition to normal diffusion on a larger time scale has been shown. Taking advantages of the NMR approach, transport properties of microemulsions consisting of micellar colloids dissolved in liquid crystals have been investigated. The self-diffusivities measured under equilibrium conditions have shown weak correlations with microscopic ordering and macroscopic phase transitions occurring in the systems under study. The formation of micelles is shown to be decisive for macroscopic separation at the isotropic-nematic transition. The second part of the thesis covers heterogeneous effects in diffusion for fluids in porous solids, as probed using a combination of NMR diffusometry and structure characterization methods. Ionic liquids have been investigated, revealing a complex behavior under confinement. The attempts to correlate the observed characteristics of the ionic liquids with their internal chemical structure were undertaken. Finally, the series of nanoporous glasses with tunable pore structure characteristics were studied. Strong correlations between their structure and the preparation conditions as well as between the resulting transport properties have been shown.

A systematic NMR cryo-porometry and -diffusometry study using nitrobenzene as a probe liquid is carried out in order to characterise pore structures of hierarchically-organised porous silica monolith possessing mesopores along with a 3D bicontinuous macropore network. The result obtained from NMR cryoporometry shows the presence of a relatively wide mesopore size distribution of 10-35 nm. Furthermore, NMR cryodiffusometry indicates that whilst the mesopores are highly tortuous (Tmeso ≈6), they have little influence on the overall tortuosity of the material (Tmacro ≈1.5), which is largely dominated by the macropores (Toverall ≈1.7).

Alterations of fluid phase transitions in porous materials are conventionally employed for the characterization of mesoporous solids. In the first approximation, this may be based on the application of the Kelvin equation for gas–liquid and the Gibbs–Thomson equation for solid–liquid phase equilibria for obtaining pore size distributions. Herein, we provide a comparative analysis of different phase coexistences measured in mesoporous silica solids with different pore sizes and morphology. Instead of comparing the resulting pore size distributions, we rather compare the transitions directly by using a common coordinate for varying the experiment’s thermodynamic parameters based on the two equations mentioned. Both phase transitions in these coordinates produce comparable results for mesoporous solids of relatively large pore sizes. In contrast, marked differences are found for materials with smaller pore sizes. This illuminates the fact that, with reducing confinement sizes, thermodynamic fluctuations become increasingly important and different for different equilibria considered. In addition, we show that in the coordinate used for analysis, mercury intrusion matches perfectly with desorption and freezing transitions.

This cumulative dissertation is a compendium of five peer-reviewed and published scientific papers on developing an advanced NMR Cryoporometry toolbox for pore architecture characterization. The dissertation contains five chapters. The first introduces porous materials, their types and applications. Chapter two describes the fundamentals of fluid phase equilibria in mesoporous solids and how modifications of the well-known Laplace equation describe various fluid phase equilibria. The basic principles of the Gas Sorption and NMR Cryoporometry techniques are discussed. In chapter three, different characterization techniques are amalgamated onto a common framework which can be used to compare fluid phase coexistence in porous materials of different pore sizes. Chapter four explains a completely new NMR Cryoporometry characterization methodology developed for cylindrical and spherical pore shapes. Chapter five concludes and crowns the present work by discussing the complementary benefits of the advanced technique in characterizing random porous materials and accounting for pore connectivity effects. All materials synthesized for the work in this dissertation have been obtained through collaborations with the groups of Profs. Dr. Michael Fröba and Simone Mascotto of the Hamburg University and Prof. Dr. Dirk Enke of the Leipzig University.:Table of Contents Thesis Summary ........................................................................................................1 List of publications ......................................................................................................2 Acknowledgements ...................................................................................................4 CHAPTER 1:.............................................................................................................10 Introduction ..............................................................................................................10 CHAPTER 2:.............................................................................................................12 Fluid Phase Equilibria in Mesoporous Solids ..........................................................12 2.1 Gas Sorption................................................................................................... 13 2.1.1 Adsorption Isotherms................................................................................ 15 2.1.2 Adsorption Hysteresis............................................................................... 18 2.1.3 Scanning Behavior.................................................................................... 23 2.2 NMR Cryoporometry ....................................................................................... 25 2.2.1 Pore Size Distribution (PSD)....................................................................... 28 2.3 Serially-Connected Pore Model (SCPM)......................................................... 29 2.4 Problem Statement ......................................................................................... 30 CHAPTER 3:..............................................................................................................32 Analogy between Characterization Techniques ......................................................32 • Publication 3. On the Comparative Analysis of Different Phase Coexistences in Mesoporous Materials CHAPTER 4:.............................................................................................................42 An Advanced NMR Cryoporometry Approach.........................................................42 • Publication 4.1. Nuclear Magnetic Resonance Cryoporometry Study of Solid−Liquid Equilibria in Interconnected Spherical Nanocages • Publication 4.2. A novel approach for advanced thermoporometry characterization of mesoporous solids: Transition kernels and the serially connected pore model CHAPTER 5:.............................................................................................................65 Characterizing Random Porous Materials................................................................65 • Publication 5.1. Comparative Gas Sorption and Cryoporometry Study of Mesoporous Glass Structure: Application of the Serially Connected Pore Model • Publication 5.2. Impact of Geometrical Disorder on Phase Equilibria of Fluids and Solids Confined in Mesoporous Materials Appendix A:.............................................................................................................100 Porous Solid Characterization Techniques............................................................100 A.1: Mercury Intrusion Porosimetry (MIP) ........................................................... 100 A.1.1. Experimental Set-up.............................................................................. 101 A.2: Gas Sorption................................................................................................ 103 A.2.1. Experimental Set-Up ............................................................................. 103 A.2: NMR Cryoporometry.................................................................................... 106 A.2.2. Experimental Set-Up ............................................................................. 106 Appendix B:..............................................................................................................109 Supporting information ............................................................................................109 Appendix C:.............................................................................................................115 Author contributions ................................................................................................115 Bibliography ............................................................................................................117

Abstract The present thesis exploits advanced liquid and gas NMR methods for the characterization of various interesting materials. The methods used to study the structural properties of thermally modified wood, ionic liquids, cements, shales, and porous organic cages include MRI, NMR cryoporometry, Laplace NMR, multidimensional Laplace NMR, as well as ¹²⁹Xe and ¹⁹F NMR. The commonality factor in all the studies is the usage of either inherent or introduced liquid or gas molecules to probe the topical materials. The MRI method was utilized to visualize the water absorption phenomena in the thermally modified pine wood. High-resolution images made it possible to observe the spatial distribution of free water and the changes in the rate of absorption of water in wood samples modified at different temperatures. The images also helped to resolve the individual resin channels. T₂ maps enabled us to observe the changes in the relaxation values of free water in thermally modified wood as compared to their unmodified reference wood samples. The multidimensional Laplace NMR methods were exploited to study the structural and dynamical properties of a novel halogen-free, boron-based ionic liquid (hf-BIL). NMR self-diffusion (D) experiments showed the presence of two coexisting dynamic phases in hf-BIL. Multidimensional D − T₂ correlation experiments made it possible to determine the T₂ relaxation times of the slow and fast diffusing phases. T₂ − T₂ relaxation exchange measurements allowed quantifying the exchange rates of anions and cations between the phases. Moreover, the theoretical modeling of the experimental data revealed that the slow diffusing phase was composed of anion-cation aggregates, while the fast diffusing phase was comprised of free anions and cations. ¹²⁹Xe NMR analysis of the xenon adsorbed in the cements and shales helped us to determine their porous structures. The method exploits the high sensitivity of the chemical shift of ¹²⁹Xe to its local environment. The chemical shift value of ¹²⁹Xe enabled us to estimate the size of the mesopores in the cement samples. The exchange spectroscopy (EXSY) measurements were used to determine the exchange rates between the free gas and mesopores of the cement samples. ¹²⁹Xe NMR spectra of the shale samples provided information about pore sizes and paramagnetic compounds. ¹H NMR cryoporometry measurements of the shale samples immersed in acetonitrile made it possible to analyze the pore size distribution ranging from 10 to over 100 nm. Moreover, T₂ − T₂ exchange measurements helped us to quantify the exchange rates of acetonitrile in the shale samples. Xenon and SF₆ were used as internal reporters to gain versatile information on adsorption phenomena in the cage and window cavities of the crystalline porous organic cages. ¹²⁹Xe NMR analysis of the adsorbed xenon helped us to determine the diffusion coefficients and activation energy of diffusion as well as thermodynamic parameters. With the help of T₂ relaxation time values, it was possible to estimate the exchange rates between cage and window cavities. Chemical exchange saturation transfer (CEST) experiments resolved a window cavity site, which arises from crystal defects in porous organic cages. In addition, ¹⁹F NMR analysis made it possible to estimate the relaxation rates and diffusion coefficients of SF₆ gas in porous organic cages. Modelling of the T₁, T₂ and diffusion data confirmed that the cage to window exchange is the completely dominating mechanism for ¹²⁹Xe T₂ relaxation. T₁ relaxation is dominated by diffusion modulated dipole-dipole relaxation (DDinter) and chemical shift anisotropy (CSA) relaxation due to local cavity mobility. Whereas, in case of SF₆ T₂ data, the dominating mechanism is diffusion modulated dipole-dipole relaxation and for T₁ the local tumbling of SF₆ in cage cavity is the key dynamics behind the dipole-dipole and CSA mechanisms. / Original papers The original publications are not included in the electronic version of the dissertation. Javed, M. A., Kekkonen, P. M., Ahola, S., & Telkki, V.-V. (2015). Magnetic resonance imaging study of water absorption in thermally modified pine wood. Holzforschung, 69(7), 899–907. https://doi.org/10.1515/hf-2014-0183 Javed, M. A., Ahola, S., Håkansson, P., Mankinen, O., Aslam, M. K., Filippov, A., … Telkki, V.-V. (2017). Structure and dynamics elucidation of ionic liquids using multidimensional Laplace NMR. Chem. Commun., 53(80), 11056–11059. https://doi.org/10.1039/c7cc05493a http://jultika.oulu.fi/Record/nbnfi-fe2017102750335 Javed, M. A., Komulainen, S., Daigle, H., Zhang, B., Vaara, J., Zhou, B., & Telkki, V.-V. (2019). Determination of pore structures and dynamics of fluids in hydrated cements and natural shales by various ¹H and ¹²⁹Xe NMR methods. Microporous and Mesoporous Materials, 281, 66–74. https://doi.org/10.1016/j.micromeso.2019.02.034 http://jultika.oulu.fi/Record/nbnfi-fe2019041712678 Komulainen, S., Roukala, J., Zhivonitko, V. V., Javed, M. A., Chen, L., Holden, D., … Telkki, V.-V. (2017). Inside information on xenon adsorption in porous organic cages by NMR. Chemical Science, 8(8), 5721–5727. https://doi.org/10.1039/C7SC01990D http://jultika.oulu.fi/Record/nbnfi-fe201709288804 Håkansson, P., Javed, M. A., Komulainen, S., Chen, L., Holden, D., Hasell, T., … Telkki, V.-V. (2019). NMR relaxation and modelling study of the dynamics of SF₆ and Xe in porous organic cages. Manuscript.

Abstract Wood is an essential material that has many applications in the fields of engineering and especially in the forest industry, which is particularly important in Fennoscandia. Among the various modification methods for wood, thermal modification has grown substantially over the past decades. It is an environmentally friendly method for increasing the lifetime and usability of timber. The aim of this thesis is to characterize the properties of thermally modified wood as well as to obtain new information on the changes taking place in pinewood due to the thermal modification process. Several NMR methods were used to gain information on the effect of thermal modification on the microstructure and moisture components of Pinus sylvestris pinewood. Pinewood samples thermally modified at different temperatures were studied and compared to corresponding unmodified wood samples. Diffusion of water and methane was studied using pulsed-field-gradient stimulated-echo measurements to determine the highly anisotropic size distribution of pores in different cell structures of pinewood. NMR cryoporometry and relaxometry measurements were conducted to gain information on the amounts and environments of both the bound and free water absorbed into the wood samples. Cryoporometry measurements resulted in an upper limit value for the size of bound water sites and the combination of cryoporometry and relaxometry data enabled the size determination of cell wall micropores. Magnetic resonance imaging was used to visualize the spatial distribution of absorbed free water in the studied samples. Together these methods give a broad overall picture of the effects of the modification process. The results of this work give new insight into the microstructure of thermally modified pinewood and its relationship to moisture, which is of importance for both wood science as well as industry. The applicability of the NMR techniques used here to the study of wood is also proven in this work. Using the techniques developed, it is possible to determine the optimal modification temperature, which is high enough to obtain the desired effects, but low enough not to destroy the microstructure of wood. / Tiivistelmä Puuta pystytään hyödyntämään useilla eri aloilla ja se on materiaalina tärkeä etenkin Fennoskandiassa merkittävälle metsäteollisuudelle. Useiden erilaisten puun käsittelymenetelmien joukossa lämpökäsittely on kasvattanut voimakkaasti suosiotaan viime vuosikymmeninä. Kyseessä on ympäristöystävällinen menetelmä, jolla voidaan pidentää puun käyttöikää sekä käytettävyyttä erilaisissa sovelluskohteissa. Tämän väitöskirjan päämääränä on ollut lämpökäsitellyn puun ominaisuuksien tutkiminen ja uuden tiedon saaminen puussa lämpökäsittelyprosessin myötä tapahtuvista muutoksista. Työssä käytettiin useita eri NMR-menetelmiä lämpökäsitellyn mäntypuun (Pinus sylvestris) mikrorakenteen sekä puussa olevan kosteuden aiheuttamien vaikutusten tutkimiseksi. Työssä tutkittiin eri lämpötiloissa käsiteltyjä mäntypuunäytteitä, joita verrattiin vastaaviin käsittelemättömiin näytteisiin. Veden ja metaanin diffuusiota tutkittiin PGSTE-menetelmällä puun erittäin anisotrooppisen solurakenteen sisältämien huokosten mittojen määrittämiseksi. NMR-kryoporometria- ja -relaksometriamittaukset antoivat tietoa puuhun imeytyneen sidotun ja vapaan veden määrästä ja esiintymisympäristöstä. Kryoporometria-mittausten tuloksista saatiin yläraja sidotun veden esiintymispaikkojen koolle, ja kryoporometria- ja relaksometriamittausten tuottaman tiedon yhdistäminen mahdollisti soluseinämien mikrohuokosten koon määrittämisen. Magneettikuvausta käytettiin näytteisiin absorboituneen veden avaruudellisen jakauman määrittämiseen. Käytetyt menetelmät tarjoavat laajan kokonaiskuvan lämpökäsittelyprosessin vaikutuksista puulle. Tämän työn tulokset antavat puutiedettä ja -teollisuutta hyödyttävää uutta tietoa lämpökäsitellyn männyn mikrorakenteesta sekä sen suhteesta kosteuteen. Väitöskirja myös osoittaa käytettyjen NMR-menetelmien soveltuvan hyvin puun tutkimiseen. Tämän tutkimuksen myötä kehitettyjen menetelmien avulla voidaan määrittää mm. optimaalinen lämpökäsittelylämpötila, joka on riittävän korkea haluttujen ominaisuuksien kannalta aiheuttamatta kuitenkaan puun mikrorakenteen hajoamista.