<p dir="ltr">The recent COVID-19 pandemic has emphasized the risk of respiratory infections leading to acute respiratory distress syndrome (ARDS). A significant factor contributing to poor ARDS outcomes is the impairment of lung surfactant due to infiltrating surface-active proteins and phospholipases during lung inflammation. Lung surfactant's vital role in stabilizing alveoli by reducing air-water interfacial tension becomes evident as its dysfunction severely compromises respiratory function. Although lung surfactant (LS) replacement therapy effectively addresses neonatal LS deficiencies, its efficacy in ARDS treatment for adults remains limited. The challenge lies in the chemical similarity between current animal-extracted surfactants and human lung surfactant which are both phospholipid-based. To address this issue, this dissertation outlines a transformative "polymer lung surfactant (PLS)" designed to overcome the limitations of conventional exogenous surfactants in treating ARDS.</p><p dir="ltr">Firstly, a formulation method, referred to as equilibration-nanoprecipitation (ENP), is established which achieves reproducibility, controls sizing, and limits dispersity of the PLS formulation consisting of block copolymer (BCP) kinetically "frozen" micelles/nanoparticles suspended in water. The method uses a two-step approach of 1) equilibrating the BCP nanoparticles in a water/co-solvent mixture and 2) removing co-solvent using dialysis against a large water reservoir. Comparison of ENP with a conventional solvent-exchange technique through experimental and computational analysis yields further insights into ENP's advantages.</p><p dir="ltr">Next, various studies are highlighted which provide fundamental characterizations of the air-water surface behavior and physical properties of BCP nanoparticles in water. The air-water surface properties of block copolymers have been studied extensively when spread as free chains in organic solvent; however, little was previously known about air-water interfacial behavior of water-spread polymer nanoparticles. The studies address such topics as the effect of nanoparticle size, effect of nanoparticle core chemistry, and the effect of temperature on surface-mechanical behavior. Insights into nanoparticle molecular structure at the interface are provided through X-ray reflectivity and grazing incidence X-ray diffraction. The effect of temperature is further characterized by developing novel NMR and Langmuir trough methods to determine the physical state (glassy vs rubbery) of the core domain in the nanoconfined state at temperatures above and below physiologic temperature.</p><p dir="ltr">Lastly, <i>in vivo </i>studies are presented which demonstrate the detailed and promising proof-of-concept results on the efficacy of the PLS technology in mouse models of lung injury. The PLS therapy not only improves biomechanical function of the lung, but it also significantly lowers the extent of lung injury as shown by histological analysis and inflammatory marker measurements. An additional <i>in vivo </i>study is presented which highlights challenges in the delivery of the liquid PLS suspension to the lungs. The <i>in vivo </i>studies ultimately provide solid motivation for continued research into the development of the PLS therapy.</p><p dir="ltr">Given the promising potential of the PLS technology shown in the <i>in vivo</i> studies, the materials characterizations shared in this presentation offer valuable insights into the design of a novel PLS therapy. From these insights, key design parameters such as nanoparticle size characteristics, core chemistry, and core molecular weight can be chosen to produce the most desirable material properties. Overall, this dissertation furthers the progress of PLS therapeutic development and will hopefully ultimately contribute to improved health outcomes in patients suffering from ARDS.</p>

No / This article describes how an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. To facilitate the design of new materials, the role of physical and chemical properties on bacterial adhesion is reviewed. The current approaches to reduce bacterial adhesion to various polymeric surfaces are discussed, as well as how multidisciplinary research on surface design and engineering may have an impact on both fundamental and applied microbiological science and technology.

No / This chapter describes the current approaches to reduce bacterial adhesion to various biomaterial surfaces, focusing on nonfouling surfaces through patterning and hydrophobicity plasma-assisted surface treatment and deposition; incorporation of antimicrobials, antibiotics, antibiofilms, and natural extracts that are either immobilized or released; dual function antimicrobial surfaces; incorporation of nonpathogenic bacteria, bacteriophages, and biofilm dispersal agents but also reduced bacterial adhesion through tissue integration. To facilitate the design of new materials, the role of physical, chemical, and biological surface properties on bacterial adhesion is reviewed in each case, as an insight into the chemical and physical cues that affect bacterial adhesion and biofilm formation can provide ideas for creating successful antifouling or antimicrobial surfaces. The application of these surfaces is explored based on the clinical needs and the market gaps. How multidisciplinary research on surface design and engineering may have an impact on both fundamental understanding of bacterial adhesion to biomaterials and applied biomaterial science and technology is finally discussed.

Understanding the supramolecular interactions governing the self-assembly of molecular building blocks upon surfaces is fundamental to the design of new devices such as sensors or catalysts. Successful heterogeneous enantioselective catalysts have relied upon the adsorption of ‘chiral modifiers’, usually chiral amino acids, onto reactive metal surfaces. One of the most researched examples is the hydrogenation of β-ketoesters using nickel-based catalysts. The stability of the chiral modifiers upon catalyst surfaces is a major obstacle to the industrial scale-up of this reaction. In this study, the replacement of conventional modifiers with porous, chiral and functionalised self-assembled networks is investigated. Perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) and melamine (1,3,5-triazine,-2,4,6-triamine) have been shown to form hydrogen bonded networks on Ag-Si(111)√3x√3R30° in ultra-high vacuum (UHV) and Au(111) substrates in UHV and ambient conditions, these networks are capable of hosting guest molecules. These networks are investigated further in this study. In UHV, the behaviour of the components and network formation on Ni(111) is probed using scanning tunnelling microscopy (STM) and temperature-programmed desorption (TPD). The stability of the PTCDI-melamine network on Au(111) was analysed using TPD. Metal coordination interactions between each of the network components and nickel upon the Au(111) surface were examined by STM before testing the ability of the network to act as a template for metal growth. Finally, a number of polymerisation reactions are investigated with a view to replacing chiral modifiers with porous, chiral, functionalised covalent networks. Periodic covalent networks should possess the greater chemical and thermal stability required for more widespread use. In UHV and ambient conditions, STM is used to monitor the progress of surface-confined reactions on Au(111) and characterise the resultant covalent structures.

Les propriétés d'une nouvelle classe de chimie de surface basée sur les monocouches auto-assemblées de liquides ioniques (ILs-SAMs), ont été étudiées pour une utilisation dans la construction de biocapteurs basés sur la résonance des plasmons de surface (SPR). Les biocapteurs sont utiles pour détecter des biomolécules spécifiques dans une matrice biologique complexe. Cependant, le signal analytique de la biomolécule spécifique peut être masqué par l’adsorption non spécifique de la matrice biologique, produisant une réponse faussement positive. Par ailleurs, l'activité des récepteurs moléculaires est souvent réduite par des techniques d'immobilisation chimique. Ainsi, il est essentiel de déterminer une surface idéale pour la préparation de biocapteurs. Les liquides ioniques sont bien connus pour favoriser l'activité des récepteurs moléculaires et cette étude enquête si cette propriété importante peut se traduire sur des capteurs SPR. Différents liquides ioniques ont été utilisés pour former des monocouches auto-assemblées sur une surface d'or. Les ILs-SAMs sont tous basés sur les sels de mercapto-(chaîne alkyle)nCH2-méthylimidazolium avec différentes chaînes alkyles (n = 3, 6, 9, 12) et différents contre-anions (Br-, BF4-, PF6-, NTf2-). Des études cinétiques de l'adsorption non spécifique de sérum bovin ont été réalisées sur des capteurs SPR avec un instrument construit sur mesure, basé sur l'interrogation des longueurs d’ondes SPR sur un prisme d’inversion d’image (dove). Par la suite, l’anti-IgG de chèvre sélective à l’IgG humain a été utilisé en tant que modèle pour la confection de biocapteurs sur les ILs-SAMs. En solution, il est possible d’effectuer des échanges du contre-anion des liquides ioniques pour un contre-anion de plus en plus hydrophobe. Cependant, l’échange inverse, soit vers des anions de plus en plus hydrophile, s’avère impossible. Toutefois, il a été observé par les travaux présentés dans ce mémoire, que les liquides ioniques immobilisés sur une surface d'or ont la capacité d'échanger leurs contre-anions réversiblement, procurant une méthode simple de moduler leurs propriétés physico-chimiques. Ce phénomène a été observé par la mesure d’angles de contacts et par les techniques spectroscopiques de l’infrarouge moyen (mid-IR), des photoélectrons de rayon-X (XPS) et par la diffusion Raman exaltée par les surfaces (SERS) ii ainsi que par la spectrométrie de masse (MS). La connaissance des propriétés d’échange d’anion est importante pour prédire le comportement de ces surfaces de liquides ioniques dans les tampons et fluides biologiques. / The properties of a novel class of surface chemistry based on ionic liquid self-assembled monolayers (IL-SAM) were investigated for use with surface plasmon resonance (SPR) biosensors. Biosensors are useful to detect specific biomolecules in a complex biological matrix. However, the analytical signal of a specific biomolecule can be masked by nonspecific adsorption of the biological matrix, resulting in a false positive response. Moreover, the activity of molecular receptors is often reduced by current immobilization chemistry. Thus, it is essential to determine an ideal surface for the preparation of biosensors. Ionic liquids are well-known to promote the activity of molecular receptors and this study investigates if this important property translates to SPR sensors. Different ionic liquids were used to form self-assembled monolayers on a gold surface. IL-SAM were based on mercapto(alkyl chain)n methylimidazolium salts with different alkyl chain (n = 3, 6, 9, 12) and counter anions (Br-, BF4-, PF6-, NTf2-). Kinetic studies of the nonspecific adsorption of bovine serum were carried on SPR sensors with a custom built instrument based on wavelength interrogation SPR on a dove prism. Thereafter, anti-goat IgG selective to human IgG was used as a model for biosensor employing ILs-SAM surface chemistry. Exchange of counter anion of ionic liquids was believed impossible for most hydrophobic counter anions. However, it was observed that ionic liquids immobilized on a gold surface have the ability to exchange their counter anions reversibly, allowing a simple method to modulate their physico-chemical properties. This phenomenon was observed by contact angle technique and by attenuated total reflectance mid-infrared (ATR mid-IR), X-ray photoelectron spectroscopy (XPS), surface enhanced raman spectroscopy (SERS) and mass spectrometry (MS). Better understanding of the anion exchange properties is crucial in predicting the behaviour of IL-SAM in presence of biological buffers and fluids.

Ion sensing represents a grand research challenge. It finds a vast variety of applications in, e.g., gas sensing for domestic gases and ion detection in electrolytes for chemical-biological-medical monitoring. Semiconductor genome sequencing exemplifies a revolutionary application of the latter. For such sensing applications, the signal mostly spans in the low frequency regime. Therefore, low-frequency noise (LFN) present in the same frequency domain places a limit on the minimum detectable variation of the sensing signal and constitutes a major research and development objective of ion sensing devices. This thesis focuses on understanding LFN in ion sensing based on both experimental and theoretical studies. The thesis starts with demonstrating a novel device concept, i.e., ion-gated bipolar amplifier (IGBA), aiming at boosting the signal for mitigating the interference by external noise. An IGBA device consists of a modified ion-sensitive field-effect transistors (ISFET) intimately integrated with a bipolar junction transistor as the internal current amplifier with an achieved internal amplification of 70. The efficacy of IGBA in suppressing the external interference is clearly demonstrated by comparing its noise performance to that of the ISFET counterpart. Among the various noise sources of an ISFET, the solid/liquid interfacial noise is poorly studied. A differential microelectrode cell is developed for characterizing this noise component by employing potentiometry and electrochemical impedance spectroscopy. With the cell, the measured noise of the TiN/electrolyte interface is found to be of thermal nature. The interfacial noise is further found to be comparable or larger than that of the state-of-the-art MOSFETs. Therefore, its influence cannot be overlooked for design of future ion sensors. To understand the solid/liquid interfacial noise, an electrochemical impedance model is developed based on the dynamic site-binding reactions of surface hydrogen ions with surface OH groups. The model incorporates both thermodynamic and kinetic properties of the binding reactions. By considering the distributed nature of the reaction energy barriers, the model can interpret the interfacial impedance with a constant-phase-element behavior. Since the model directly correlates the interfacial noise to the properties of the sensing surface, the dependencies of noise on the reaction rate constants and binding site density are systematically investigated.

The initiation and high resolution control of surface confined chemical reactions would be both beneficial for nanofabrication and fundamentally interesting. In this work, spatially controlled scanning probe directed organometallic coupling, patterned functional protein immobilisation and highly localised reversible redox reactions on SAMs were investigated. Catalytically active palladium nanoparticles were mounted on a scanning probe and an appropriate reagent SAM was scanned in a reagent solution. This instigated a spatially resolved organometallic coupling reaction between the solution and SAM-phase reagents. Within this catalytic nanolithography a spatial resolution of ~10nm is possible, equating to zeptomole-scale reaction. The methodology was applied to reactions such as Sonogashira coupling and local oligo(phenylene vinylene) synthesis. By altering the experimental protocols, relating probe scan velocity to reaction yield and characterising the nanopattern, a PVP matrix model describing a proposed mechanism of catalytic nanolithography, was presented. Though ultimately limited by probe deactivation, calculations indicated that activity per immobilised nanoparticle is very high in this configuration. For biopatterning, surface nanopatterns defined by carboxylic functionality were generated from methyl-terminated SAMs by local anodic oxidation (LAO) initiated by a conductive AFM probe. By employing suitable linker compounds, avidin and Stefin-A quadruple Mutant (SQM) receptive peptide aptamers were patterned at sub-100nm resolution. The multiplexed sensing capability of an SQM array was demonstrated by reacting generated patterns with single or a mixture of multiple antibodies. The reversible redox conversion and switching of reactivity of hydroquinone-terminated SAMs was electrochemically demonstrated prior to an application in redox nanolithography. In this methodology, spatially controlled probe-induced in situ "writing" and "erasing" based on reversible redox conversion were conducted on hydroquinone terminated SAM. In combination with dip-pen nanolithography, a novel method of redox electro-pen nanolithography was designed and the method’s application for lithography was examined.

This thesis reports on the elemental growth of oxide thin films including TiO_x, BaO_x and Ba_xTi_yO_z by Ti/Ba deposition and oxidation. The films were grown on two different substrates, Au(111) and SrTiO₃(001), and studied using a variety of surface characterisation techniques. On the reconstructed Au(111) surface, three different TiO_x structures were obtained with increasing Ti amounts deposited: a (2 × 2) Ti₂O₃ honeycomb structure, a pinwheel structure that is the result of a Moiré pattern, and a triangular island TiO_1.30 structure. The structures arise from raised Ti coverages and have increased Ti densities. Although Ba deposited on the reconstructed Au(111) has a weak interaction with the substrate, the BaO_x thin films can grow epitaxially and lift the Au(111) reconstruction. Two well-ordered phases, a (6 × 6) and a (2√3 × 2√3) BaO_x structure, were obtained which may have octopolar-based surface structures. For Ba & Ti deposition on Au(111), a locally ordered (5 × 5) BaxTiyOz structure was observed in the sub-monolayer regime. What is more interesting is the possible formation of a BaO-TiO surface alloy with short-range ordering achieved by Ba deposition on the (2 × 2) Ti₂O₃-templated Au(111) surface. This is the first time that surface-alloying has been observed for oxides. When Ti is deposited onto the SrTiO₃(001) surface, it is incorporated into the substrate by forming a variety of Ti-rich SrTiO₃ surface reconstructions, such as c(4 × 2), (6 × 2), (9 × 2) and (√5 ×√5)-R26.6°. Ti deposition provides a completely different route to obtaining these reconstructions at much lower anneal temperatures than the previously reported preparation procedures involving sputtering and annealing the SrTiO₃ sample. Anatase islands with (1 × 3) and (1 × 5) periodicities were also formed by increasing the Ti deposition amount and post-annealing. Reconstructed SrTiO₃ substrate surface has a lattice that differs from the bulk crystal and affects the epitaxial growth of BaO, however, a locally ordered BaO_x structure was observed on the sputtered substrate with a growth temperature of 300 °C. Depositing Ba & Ti on SrTiO₃(001) results in the formation of BaO_x clusters and the Ti incorporation into the substrate, forming the familiar Ti-rich SrTiO₃ surface reconstructions.

Electrochemistry is the science of electron transfer. The subject is of great importance and appeal because detailed information can be obtained using relatively simple experimental techniques. In general, the raw data is sufficiently complicated to preclude direct interpretation, yet is readily rationalised using numerical procedures. Computational analysis is therefore central to electrochemistry and is the main topic of this thesis. Chapters 1 and 2 provide an introductory account to electrochemistry and numerical analysis respectively. Chapter 1 explains the origin of the potential difference and describes its relevance to the thermodynamic and kinetic properties of a redox process. Voltammetry is introduced as an experimental means of studying electrode dynamics. Chapter 2 explains the numerical methods used in later chapters. Chapter 3 presents a review of the use of nanoparticles in electrochemistry. Chapter 4 presents the simulation of a random array of spherical nanoparticles. Conclusions obtained theoretically are experimentally confirmed using the Cr³⁺/Cr²⁺ redox couple on a random array of silver nanoparticles. Chapter 5 presents an investigation into the concentration of supporting electrolyte required to make a voltammetric experiment quantitatively diffusional. This study looks at a wide range of experimental conditions. Chapter 6 presents an investigation into the deliberate addition of insufficient supporting electrolyte to an electrochemical experiment. It is shown that this technique can be used to fully study a stepwise two electron transfer. Conclusions obtained theoretically are experimentally confirmed using the reduction of anthracene in acetonitrile. Chapter 7 presents a new method for simulating voltammetry at disc shaped electrodes in the presence of insufficient supporting electrolyte. It is shown that, under certain conditions, the results obtained from this complicated simulation can be quantitatively obtained by means of a much simpler ‘hemispherical approximation’. Conclusions obtained theoretically are experimentally confirmed using the hexammineruthenium ([Ru(NH₃)₆]³⁺/[Ru(NH₃)₆]²⁺) and hexachloroiridate ([IrCl₆]²⁻/[IrCl₆]³⁻) redox couples. Chapter 8 presents an investigation into the voltammetry of stepwise two electron processes using ionic liquids as solvents. It is shown that these solvents can be used to fully study a stepwise two electron transfer. Conclusions obtained theoretically are experimentally confirmed using the oxidation of N,N-dimethyl-p-phenylenediamine in the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([C₄ mim][BF₄]). The work presented in this thesis has been published as 7 scientific papers.

The development of a clean hydrogen economy will aid a smooth transition from fossil fuels which is required to stem the environmental impact and economic instability caused by oil dependency. For vehicular application, in addition to being cheap and safe, a commercial hydrogen store must contain a certain weight percentage of hydrogen to provide a reasonable range (~300 miles). It must also be able to release hydrogen under near-ambient conditions (80-120°C) and have a reasonable cycling capacity (~1000 cycles). The primary motivation of this thesis is to gain a fundamental understanding into the sorption processes of hydrogen on carbon- and aluminium-based materials to improve their hydrogen storage capacity. The sorption processes of hydrogen on mechanically milled graphite have been investigated, primarily using Electron Spin Resonance Spectroscopy and Inelastic Neutron Scattering. An investigation into the storage properties of tetrahydroaluminates, primarily NaAlH₄ and LiAlH₄, is performed in the presence and absence of a catalyst, and a new phase of NaAlH₄ is observed prior to its decomposition. Variable temperature neutron and synchrotron diffraction, in conjunction with gravimetric and mass spectroscopy data were obtained for several mixtures of tetrahydroaluminates and alkali amides and the hydrogen desorption processes are shown to be quite different from the constituent materials. The structure of Ca(AlH₄)₂ has been experimentally determined for the first time and a complete set of equations describing its decomposition pathway is given.