<p>  </p> <p>Experimental and computational techniques are used to study physico-chemical phenomena occurring in water on which hydrophobic interactions play a role. In particular, hydrophobic self-aggregation, including host-guest binding, and the affinity of ions to oil/water interfaces are investigated. Raman multivariate curve resolution (Raman-MCR) spectroscopy was the experimental technique used to unveil intermolecular interactions through the analysis of solute-correlated (SC) vibrational spectra. Molecular simulations, including molecular dynamics (MD) simulations, quantum-mechanical calculations, or a combination of both, were carried out to assist with the molecular-level interpretation of the experimental SC spectra.</p>

<p>Extracellular matrix (ECM) creates high-resolution chemical patterns, by assembling simple molecules with nm-scale features (e.g., carbohydrates, nucleotides, amino acids) into complex structures up to micrometers and extending to even larger scales across tissues (e.g., glycans, DNA, proteins), capable of carrying out the diverse and complex cellular functions. Mimicking the complexity of such biological systems requires precise control over the chemical patterning on substrates that exhibit physiochemical properties similar to biological systems (such as hydrogels). Although hydrogels provide tunable physiochemical properties suitable for biological applications; it is a porous material where pore sizes can range from 30 nm to greater than 1000 nm. Due to this structural heterogeneity, chemical patterning below the length scale of this heterogeneity is very challenging.</p> <p>Here, we demonstrate a new assembly system for generating a nanostructured presentation of carbohydrates on the hydrogel surface. This approach is based on the striped phases assembly of functional alkanes where 1-nm resolution functional patterns are readily assembled on substrates such as highly ordered pyrolytic graphite (HOPG). In this assembly, molecules are stabilized by noncovalent interactions, including alkyl-pi interactions underlying the HOPG, van der Waals interaction between the adjacent alkyl chains, and hydrogen bonding between polar head groups. Topochemical polymerization converts internal diynes into conjugated polydiacetylenes (PDAs). PDAs can also be utilized to covalently attach the striped pattern to polyacrylamide hydrogels through free radical chemistry.</p> <p>Here, we synthesize new amphiphiles with carbohydrate headgroups (N-acetyl-D-glucosamine (GlcNAc), and D-glucuronic acid (GlcA)), assembled into striped phases on HOPG and covalently transfer to polyacrylamide hydrogels. GlcNAc binds to wheat germ agglutinin (WGA), a lectin that binds specifically in a multivalent fashion (dissociation constant KD in nm range) to GlcNAc. We show that GlcNAc striped phases generate highly selective interactions with wheat germ agglutinin (WGA) but do not induce specific binding with concanavalin A (another lectin molecule that does not target GlcNAc). We further demonstrate that WGA binding affinity can be modulated by shifting the position of diacetylenes that bring the polymer backbone closer to the GlcNAc, increasing the effecting local concentration of carbohydrates.</p> <p>We investigated the possibility of using sPDA for secondary functionalization with complex biological molecules (such as biotin and cRGD) to mimic the ECM composition closely. The unusual reactivity of the sPDA backbones during the covalent transfer of the striped phase monolayer to hydrogels illustrates the potential of sPDA reactivity azides. In this work, we show that the addition of substituted azide molecules to sPDA-functionalized hydrogels produces a decrease in the fluorescence of the sPDA monolayer. Since these reactions are occurring on porous hydrogel surfaces characterization using techniques such as IR or NMR is difficult. We carried out further solution-phase reactions using a soluble PDA where PDA UV-vis absorption spectra red-shift after the reaction between the PDA backbone and azide. These experiments support the hypothesis of sPDA and azide click reaction.</p>

No description available.

<p dir="ltr">Directed hydrogenation, in which product geometric selectivity is dictated by the binding of an ancillary directing group on the substrate to the catalyst, is typically achieved by homogeneous Rh and Ir complexes. No heterogeneous catalyst has been able to achieve equivalently high directivity due to a lack of control over substrate binding orientation at the catalyst surface. In this work, we demonstrate through structure-activity studies that careful control of surface ensemble geometry in bimetallic nanoparticle catalysts can confer hydroxyl-directed selectivity in heterogeneous double bond hydrogenation. We postulate that the oxophilic alloy component binds hydroxyl groups to pre-orient the molecule on the surface, while proximal noble metal atoms impart facially selective addition of hydride to the olefin. We found that controlling the degree of surface alloying between oxophilic and noble metal component as well as alloy component identity is critical to maximizing reaction selectivity and starting material conversion. Our optimized catalysts exhibit good functional group tolerance on a variety of cyclohexenol and cyclopentenol scaffolds, with Pd-Cu and Pt-Ni systems being developed for the diastereoselective hydrogenation of tri- and more challenging tetra-substituted olefins, respectively. The applicability of this method is then demonstrated in a four-step synthesis of a fine fragrance compound, (1<i>R</i>,2<i>S</i>)-(+)-<i>cis</i>-methyldihydrojasmonate (Paradisone®), with high yield and enantiopurity.</p>

<p>This dissertation describes how the surface chemistries of 2D nanomaterials can be modified to alter overall material properties. Specifically, through a focus of the ligand-surface atom bonding in addition to the overall ligand structure we highlight the ability to direct morphological outcomes in lead free halide perovskites, maximize optoelectronic responses in substoichiometric tungsten oxide, and alter physicochemical properties titanium carbide MXenes.   </p>

The aim of this thesis work was to gain understanding of the interactions between talc mineral and surfaces, liquids and chemicals relevant for industrial applications, such as pulp and paper. Talc is used in the pulp and paper industry as a filler pigment, in control of pitch (lipophilic extractives) deposits and as a coating pigment. A deeper understanding of talc interactions will be beneficial in optimizing its use. Long-range attractive interactions between talc and hydrophobic model probes, as well as pitch probes, have been measured using the atomic force microscope (AFM) colloidal probe method. Two procedures for preparation of pitch colloidal probes were developed to allow these studies. Model hydrophobic, nanorough surfaces with surface energy characteristics similar to talc have also been prepared and their interactions with hydrophobic model probes compared to interactions between hydrophobic model probes and talc. It is demonstrated that talc mineral interacts with model hydrophobic particles, as well as with pitch, by long-range attractive forces, considerably stronger than the expected van der Waals force. The possible origin of the measured interaction forces is discussed, and the conclusion is that the main cause is an attractive capillary force due to formation of a gas/vapor capillary between the surfaces. Force measurements using model hydrophobic, nanorough surfaces show that a large-scale waviness does not significantly influence the range and magnitude of the capillary attraction, but large local variations in these quantities are found. It is demonstrated that a large variation in adhesion force corresponds to a small variation in local contact angle of the capillaries at the surfaces. The nature of the surface topographical features influences the capillary attraction by affecting the local contact angle and by pinning of the three-phase contact line. The effect is clearly dependent on the size of the surface features and whether they exist in the form of crevices or as extending ridges. Entrapment of air also affects the imbibition of water in pressed talc tablets. The effects of wetting and dispersion agents on the interactions between talc and hydrophobic probes have also been investigated. It is demonstrated that a common dispersing agent used for talc, poly(acrylic acid), does not affect the capillary attraction between talc and non-polar probes. In fact, the results strongly suggest that poly(acrylic acid) does not adsorb on the basal plane of talc. From this finding it is inferred that the stabilizing effect of this additive most likely is due to adsorption to the edges of talc. In contrast, a wetting agent (the non-ionic triblock copolymer Pluronic PE6400) removes the long-range capillary attraction. It is suggested that such an ability to replace air at the talc surface is of great importance for an efficient wetting agent. The Hamaker constant for talc has also been estimated by using optical data obtained from spectroscopic ellipsometry. It is demonstrated that a nanocrystalline talc mineral, cut in different directions displays very small differences in Hamaker constant between the different crystallographic orientations, whereas a microcrystalline sample displays a significantly higher value. The estimated Hamaker constants are discussed for different material combinations of relevance for the pulp- and paper industry, such as cellulose and calcium carbonate. / Målet med detta avhandlingsarbete var att öka förståelsen för interaktioner mellan talkmineral och ytor, vätskor och kemikalier relevanta för industriella applikationer, såsom papper och massa. Talk används i pappers- och massaindustrin som fyllmedel, för kontroll av hartsrika (lipofila extraktivämnen) avsättningar och som bestrykningspigment. En djupare förståelse för talkinteraktioner kommer att vara användbart för att optimera dess användning. Långväga attraktiva interaktioner mellan talk och hydrofoba modellpartiklar, såväl som mellan talk och hartspartiklar, har uppmätts med hjälp av atomkraftsmikroskopi (AFM) genom att fästa kolloidala partiklar på kraftsensorn. Två metoder för att framställa partiklar gjorda av harts har utvecklats för att möjliggöra dessa studier. Hydrofoba, nanostrukturerade modellytor med ytenergier liknande de för talk har också tillverkats och deras växelverkan med hydrofoba modellpartiklar har jämförts med dem mellan talk och hydrofoba modellpartiklar. Studierna visar att talkmineral växelverkar med hydrofoba modellpartiklar, såväl som med harts, genom långväga attraktiva krafter som är betydligt starkare än den förväntade van der Waals kraften. Möjliga orsaker till de uppmätta växelverkanskrafterna diskuteras och slutsatsen blir att huvudorsaken är en attraktiv kapillärkraft som uppkommer genom att en gas-/ångkapillär bildas mellan ytorna. Kraftmätningar gjorda med hydrofoba nanostrukturerade modellytor visar att en storskalig vågighet inte nämnvärt påverkar storleken av kapillärattraktionen, men stora lokala variationer existerar. Det demonstreras att en stor variation i adhesionskraft motsvaras av en liten variation i lokal kontaktvinkel för kapillärerna på ytorna. Ytornas topografi påverkar kapillärattraktionen genom att påverka den lokala kontaktvinkeln samt genom att trefaskontaktlinjen inte kan röra sig fritt över ytan. Effekten är tydligt beroende av huruvida ytojämnheterna existerar i form av nedsänkningar eller upphöjningar. Instängd luft påverkar också pressade talktabletters uppsugningsförmåga av vatten. Vätnings- och dispergeringsmedels inverkan på växelverkan mellan talk och hydrofoba partiklar har undersökts. Resultaten visar att ett vanligt dispergeringsmedel för talk, polyakrylsyra, inte påverkar kapillärattraktionen. I själva verket tyder data på att polyakrylsyra inte adsorberas på talks basalplan. Utifrån dessa resultat dras slutsatsen att polyakrylsyra stabiliserar talkdispersioner genom att adsorbera på talkkanterna. Ett vanligt vätmedel (nonjonisk triblock sampolymer Pluronic PE6400) tar å andra sidan bort långväga kapillärattraktion. Detta antyder att egenskapen att ersätta luft på talkytan är av stor betydelse för effektiva vätmedel. Hamakerkonstanten för talk har uppskattats genom att utnyttja optiska data från ellipsometrimätningar. Det demonstreras att ett nanokristallint talkmineral kapat i olika riktningar uppvisar mycket små skillnader i Hamakerkonstant mellan de olika kristallografiska orienteringarna, medan ett mikrokristallint prov uppvisar ett betydligt högre värde. De beräknade Hamakerkonstanterna diskuteras för olika materialkombinationer relevanta för pappersindustrin, såsom cellulosa och kalciumkarbonat. / QC 20100813

This thesis describes the synthesis and characterisation of titania photocatalysts for incorporation into a polyethylene film. Monodisperse, anatase-phase titania nanoparticles are prepared and the synthesis conditions necessary for attraction to a laponite clay support are determined. Methods of preventing agglomeration of the laponite system such as the use of a polyethylene oxide surfactant or chemical modification of the laponite plate edges with a dimethyloctyl methoxysilane are also explored. Finally, photocatalytic studies on the laponite-supported titania nanoparticles are performed, and the compatibility and photoactivity of these materials in the polyethylene film are examined.

Persistent organic pollutants (POPs) are hydrophobic substances that readily sorb to organic matter in particles and colloids instead of being freely dissolved in the water phase. This sorption affects the bio­availability and environmental transport of the POPs. The major part of this thesis concerns the role of sediments as secondary sources of POPs. As the primary emissions decrease, contaminated sediments where POPs have accumulated can become the main source of contamination. If the contaminated sediment by time becomes covered with cleaner layers, the POPs are buried and no longer in contact with the aquatic environment. Experiments in this thesis showed, however, that new invading species can alter the sediment-water dynamics as a result of their bioturbation, i.e. mixing of sediment particles and pore-water. Marenzelleria spp., invading species in the Baltic Sea that burrow deeper than native species, were found to increase the remobilization of buried contaminants. The sediment-to-water flux was inversely related to the burial depth (2-10 cm) of the POP congeners (polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers) and also inversely related to the hydrophobicity of the congener. The flux was therefore most pronounced for less hydrophobic contaminants, which was linked to the bioirrigating behaviour of these species. Marenzelleria spp. also accumulated the buried POPs and increased concentrations in surface sedi­ment. Contaminants previously considered buried at a ’safe’ depth can thus be remobilized as a result of the invasion of Marenzelleria spp. in the Baltic Sea. One method to decrease the remobilization of contaminants from sediments is ’capping’, i.e. a layer of clean material is placed as a cap on the sediment. By amending the cap with active materials, which sequester the POPs and decrease their availability, thinner layers can be used (’active capping’ or ’thin-layer capping’). Results from an experiment with thin-layer capping using different active materials (activated carbon (AC) and kraft lignin) showed that both the sediment-to-water flux and the bioaccumulation by benthic species of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), hexachlorobenzene (HCB) and octachlorostyrene (OCS) decreased with increased thick­ness of the cap layer (0.5-5 cm). Amendments with active materials further increased the cap efficiency. AC was more efficient than kraft lignin, and a 3 cm cap with 3.3% AC reduced the flux and bioaccumulation with ~90%. The reduction of the sediment-to-water flux was inversely related to the hydrophobicity of the POP, and reductions in the flux had similar magnitudes as reductions in the concentration in deep-burrowing polychaetes, demonstrating the importance of bioturbation for sediment-to-water transport. In a one-year study on the levels of PCDD/Fs, PCBs, and HCB in a coastal area of the Baltic Sea, the correlations between the POP levels and the levels of particles and organic carbon in the water were found to differ for POPs of different structure and hydrophobicity. The levels of PCDD/Fs decreased to one third in May, which could be related to the increased sedimentation, i.e. water-to-sediment transport, during spring bloom.

Do metal particles (including particles of pure metals, alloys, metal oxides and compounds) pose a hazard or risk to human health? In the light of this question, this thesis summarizes results from research conducted on metal particles, and describes the elaboration and implementation of an in vitro test methodology to study metal release from particles through corrosion and dissolution processes in synthetic biological media relevant for human exposure through inhalation/ingestion and dermal contact. Bioaccessible metals are defined as the pool of released metals from particles that potentially could be made available for absorption by humans or other organisms. Studies of bioaccessible metals from different metal particles within this thesis have shown that the metal release process is influenced by material properties, particle specific properties, size distribution, surface area and morphology, as well as the chemistry of synthetic biological test media simulating various human exposure scenarios. The presence of metal particles in proximity to humans and the fact that metals can be released from particles to a varying extent is the hazard referred to in the title. The bioavailable metal fraction of the released metals (the fraction available for uptake/absorption by humans through different exposure routes) is usually significantly smaller than the bioaccessible pool of released metals, and is largely related to the chemical form and state of oxidation of the released metals. Chemical speciation measurements of released chromium for instance revealed chromium to be complexed to its non-available form in simulated lung fluids. Such measurements provide an indirect measure of the potential risk for adverse health effects, when performed at relevant experimental conditions. A more direct way to assess risks is to conduct toxicological in-vitro testing of metal particles, for instance on lung cell cultures relevant for human inhalation. Induced toxicity of metal particles on lung cells includes both the effect of the particles themselves and of the released metal fraction (including bioaccessible and bioavailable metals), the latter shown to be less predominant. The toxic response was clearly influenced by various experimental conditions such as sonication treatment of particles and the presence of serum proteins. Thorough characterization of metal particles assessing parameters including chemical surface composition, degree of agglomeration in solution, size distribution, surface area and morphology was performed and discussed in relation to generated results of bioaccessibility, bioavailability and induced toxicity. One important conclusion was that neither the surface composition nor the bulk composition can be used to assess the extent of metals released from chromium-based alloy particles. These findings emphasize that information on physical-chemical properties and surface characteristics of particles is essential for an in-depth understanding of metal release processes and for further use and interpretation of bioaccessibility data to assess hazard and reduce any risks induced by human exposure to metal particles. / QC 20100803

The theory of Brownian motion is a cornerstone of modern physics. In this thesis, we introduce a nonequilibrium extension to this theory, namely an effective Markovian theory of the Brownian motion of a heated nanoparticle. This phenomenon belongs to the class of nonequilibrium steady states (NESS) and is characterized by spatially inhomogeneous temperature and viscosity fields extending in the solvent surrounding the nanoparticle. The first chapter provides a pedagogic introduction to the subject and a concise summary of our main results and summarizes their implications for future developments and innovative applications. The derivation of our main results is based on the theory of fluctuating hydrodynamics, which we introduce and extend to NESS conditions, in the second chapter. We derive the effective temperature and the effective friction coefficient for the generalized Langevin equation describing the Brownian motion of a heated nanoparticle. As major results, we find that these parameters obey a generalized Stokes–Einstein relation, and that, to first order in the temperature increment of the particle, the effective temperature is given in terms of a set of universal numbers. In chapters three and four, these basic results are made explicit for various realizations of hot Brownian motion. We show in detail, that different degrees of freedom are governed by distinct effective parameters, and we calculate these for the rotational and translational motion of heated nanobeads and nanorods. Whenever possible, analytic results are provided, and numerically accurate approximation methods are devised otherwise. To test and validate all our theoretical predictions, we present large-scale molecular dynamics simulations of a Lennard-Jones system, in chapter five. These implement a state-of-the-art GPU-powered parallel algorithm, contributed by D. Chakraborty. Further support for our theory comes from recent experimental observations of gold nanobeads and nanorods made in the the groups of F. Cichos and M. Orrit. We introduce the theoretical concept of PhoCS, an innovative technique which puts the selective heating of nanoscopic tracer particles to good use. We conclude in chapter six with some preliminary results about the self-phoretic motion of so-called Janus particles. These two-faced hybrids with a hotter and a cooler side perform a persistent random walk with the persistence only limited by their hot rotational Brownian motion. Such particles could act as versatile laser-controlled nanotransporters or nanomachines, to mention just the most obvious future nanotechnological applications of hot Brownian motion.