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A full understanding of chemical reaction dynamics at the gas/organic-surface interface requires knowledge of energy-transfer processes that happen during the initial gas/surface collision. We have examined the influence of mass and rovibrational motion on the energy-transfer dynamics of gas-phase species scattering from model organic surfaces using theory and experiment. Molecular-beam scattering techniques were used to investigate the rare gases, Ne, Ar, Kr, and Xe, and the diatomics, N₂ and CO, in collisions with CH₃- and CF₃-terminated self-assembled monolayer (SAM) surfaces. Complementary molecular-dynamics simulations were employed to gain an atomistic view of the collisions and elucidate mechanistic details not observable with our current experimental apparatus. We developed a systematic approach for obtaining highly accurate analytic intermolecular potential-energy surfaces, derived from high-quality ab initio data, for use in our classical-trajectory simulations. Results of rare gas scattering experiments and simulations indicate mass to be the determining factor in the energy-transfer dynamics, while other aspects of the potential-energy surface play only a minor role. Additionally, electronic-structure calculations were used to correlate features of the potential-energy surface with the energy-transfer behavior of atoms and small molecules scattering from polar and non-polar SAM surfaces. Collisions of diatomic molecules with SAMs are seen to be vibrationally adiabatic, however translational energy transfer to and from rotational modes of the gas species, while relatively weak, is readily apparent. Examination of the alignment and orientation of the final rotational angular momentum of the gas species reveals that the collisions induce a stereodynamic preference for the expected "cartwheel" motion, as well as a surprising propensity for "corkscrew" or "propeller" motion. The calculated stereodynamic trends suggest that the CH₃-SAM is effectively more corrugated than the CF₃-SAM. Finally, the feasibility for collisional-energy promoted, direct gas/organic-surface reactions was interrogated using the 1,3-dipolar azide-alkyne cycloaddition reaction. We found that geometrical constraints prevented the reaction from proceeding at the probed conditions. / Ph. D.

Technological advances require novel solutions for contactless energy transfer. Many engineering applications require unique approaches to power electrical components without using physical wires. In the past decade, awareness of the need to wirelessly power electrical components spawned many forays into the field of wireless power transfer (WPT). WPT techniques include capacitive energy transfer, electromagnetic inductive power transfer, electromagnetic radiative power transfer, electrostatic induction, and acoustic energy transfer. Acoustic energy transfer (AET) has many advantages over other methods. These advantages include lower operating frequency, shorter wavelengths enabling the use of smaller sized receiver and transmitter, extended transmitter-to-receiver distance therefore more manageable design constraints, achieving lower attenuation, higher penetration depth, and no electromagnetic losses. Most AET systems operate in the ultrasonic frequency range and are more commonly referred to as ultrasonic acoustic energy transfer (UAET) systems. Through-wall UAET systems are constructed of a transmitter bonded to a transmission elastic layer, which in turn is bonded to a receiver. The transmitter and receiver layers are constructed of a piezoelectric material. Piezoelectric materials behave according to the piezoelectric effect, which is when a material generates an electric charge in response to mechanical strain. The transmitter utilizes the reverse of the piezoelectric effect. A sinusoidal input voltage is applied to the transmitter, inducing vibrations in the transmitter. The vibration-induced acoustic waves emanating from the transmitter travel through the initial bonding layer, the transmission layer, and the final bonding layer to the receiver. In turn, the acoustic waves cause the receiver to deform and undergo strain. This induces a flow of charge in the receiver, which is an electric current. The receiver feeds current to a resistive load. In this manner, energy is acoustically transferred between two transducers without wires. The performance of UAET systems can be evaluated based on power transfer efficiency, voltage magnification, and input admittance. UAET systems require extensive modeling before experimental assembly can be attempted. The analytical models of UAET are either based on the mechanics of the constitutive relations of piezoelectricity and solid mechanics or using equivalent circuit methods. The equivalent circuit method approximates the physics of the UAET system with electrical assumptions. The mechanics-based method is the most comprehensive description of the physics of all the intermediate layers in a UAET system. The mechanics-based method has been based on the assumption that the UAET system is operated in the thickness mode of vibration, i.e., piston-like vibration mode where the transmitter and receiver disks vibrate only in the thickness direction. This poses an issue for disks with aspect ratios between 0.1 and 20 because the piezoelectric transducers vibrate in both the radial and thickness modes. In addition to this assumption, most of the works on UAET models only have accounted for the piezoelectric and transmission layers. The effects of the bonding layers were not considered. Bonding the piezoelectric layers to the transmission layer introduces epoxy material with mechanical properties that are not accounted for. The epoxy layers are extra barriers to the transmission that introduce attenuation and alter the vibrational and acoustical behaviors of the UAET system. Investigations into UAET commonly focus on metal through-wall applications. Alternate transmission layer materials are not investigated and the impact of varying mechanical properties on the performance of a through-wall UAET system has not been comprehensively studied. Even with the metal transmission layers, the impact of the metal thickness has not been extensively investigated thoroughly. This work addresses the issues of the thickness-mode assumption in UAET modeling, the effects of epoxy layers, the impacts of the metal layer geometry, and the performance of UAET systems with alternate transmission layer materials. Particularly, (1) we showed that the thickness-mode assumption, that has been used in the UAET modeling leads to inaccurate results. (2) We modified the available acoustic electro- elastic theoretical modeling to include the effects of radial modes as well as the epoxy bonding layers. (3) We showed that the geometry of the elastic/metal layer requires optimization for peak system efficiency. (4) The results show that using alternate transmission layer materials impacts the performance of UAET systems. The results of this work were investigated using an improved 5-layer analytical model and finite element modeling in COMSOL Multiphysics. / Master of Science / Wireless power transfer (WPT) is an innovative solution to the problem of powering sophisticated technological applications. Such instances include the powering of implanted medical devices, recharging inaccessible sensor networks, and wireless powering of components in sealed containers. Acoustic energy transfer (AET) is a feasible WPT method that addresses these needs. AET is based on the propagation of acoustic waves to a piezoelectric receiver which converts the vibrations caused by incident acoustic waves into electrical energy. Most AET systems operate in the ultrasonic frequency range, and so AET can also be referred to as ultrasonic acoustic energy transfer (UAET). Through-wall UAET systems are constructed from a transmitter that is bonded to a transmission elastic layer. The transmission layer is bonded to a receiver. The transmitter and receiver are made of a piezoelectric material. This thesis addresses the modeling process of through-wall UAET systems. In previous works, the fundamental assumption has been that such systems vibrate purely in the thickness mode. Additionally, other investigations did not comprehensively analyze the effects of the bonding layers, ascertain the performance of non-metal transmission layers, or provide practical insight on the effect of the resistive loading on such systems. This work addresses all these issues with a mathematical framework and finite element modeling results.

No / We describe a series of experiments designed to investigate the conformational transition that highly-branched polymers with ligands undergo when interacting with bacteria, a process that may provide a new sensing mechanism for bacterial detection. Fluorescent highly-branched poly(N-isopropyl acrylamide)s (HB-PNIPAM) were prepared by sequential self-condensing radical copolymerizations, using anthrylmethyl methacrylate (AMMA) and fluorescein-O-acrylate (FA) as fluorescent comonomers and 4-vinylbenzyl pyrrole carbodithioate as a branch forming monomer. Differences in reactivity necessitated to first copolymerize AMMA then react with FA in a separate sequential monomer feed step. Modifications of the chain ends produced vancomycin-functional derivatives (HB-PNIPAM-Van). The AMMA and FA labels allow probing of the conformational behaviour of the polymers in solution via Forster resonance energy transfer experiments. It was shown that interaction of this polymer's end groups with Staphylococcus aureus induced a macromolecular collapse. The data thus provide conclusive evidence for a conformational transition that is driven by binding to a bacterium.

Electronic energy transfer has been investigated in pure donor systems by means of computer simulations. Calculated properties were the probability that the initially excited donor is excited at a time t after the excitation, Gs(t), the mean square displacement of the excitation and different fluorescence observables. For three dimensional systems the results obtained by Monte Carlo simulations were compared to the so-called GAF-theory {Gouchanour,C. R., Andersen, H. C. and Fayer, M. D., J. Chem. Phys. 81, 4380 (1984)}, and the agreement was found to be good. Anisotropic systems, i.e. mono-, bi- and multilayer systems, were compared to the two-particle model {Baumann,J. and Fayer, M. D., J. Chem. Phys. 85, 4087 (1986)}. The agreement between the Gs(t) calculated from the tp- model and the Monte Carlo simulations were good for all systems investigated. However, the agreement between the fluorescence observables obtained by MC and the tp-model were in general poor. A much better agreement was found when a phenomenological approach was used for calculating the fluorescence depolarization ratios. Three dimensional systems where the donors are rotating on the same time scale as the energy transfer takes place have also been studied and compared to analytical theories. The Molecular Dynamics simulations of decapeptide H142 shows that simulations in a continuum with a relative permeability do not provide a reliable alternative to simulations with explicit solvent molecules. / <p>Diss. (sammanfattning) Umeå : Umeå universitet, 1991, härtill 5 uppsatser</p> / digitalisering@umu

This research has its basis in developments within the field of inductive powering and wireless power transfer, WPT, and more specifically one the branch within this field, which is called magnetic resonance coupling. This principle enables efficient power transfer from a transmitting unit to a receiving unit at a distance of some times the unit diameter. The developments within magnetic resonant coupling are together with the possibilities and challenges of today’s smart textile industry the starting point to investigate a novel textile-based product concept for WPT by combining both technologies. Multiple textile samples, consisting of cotton and electrically conductive copper yarns, were produced by weaving technique, additional assembling of electronic components were performed manually and several measurements were carried out to investigate the sample characteristics and the sample performance in terms of power transfer. The produced samples showed to behave similarly to conventional inductors and were able to transfer power over some distance.

The aim of this thesis is to design a kilowatt three-phase step-down rotary transformer for a permanent magnet DC motor. The permanent magnet DC motor has an on-rotor drive system, and therefore requiring a power supply that can transfer power to its drive unit without mechanical contact. The rotary transformer has a detached magnetic coupling structure that qualifies it as a potential method for the wireless power transfer. This thesis studies the rotary transformer as a static device, focusing on its core loss. By using a transient finite element analysis of COMSOL Multiphysics and an iron loss prediction model, the rotary transformer was optimized in terms of efficiency and power density for the on-rotor drive system through proper material selection and geometry exploration. After this, a mechanical design, which based on a literature review of the influences of manufacturing processes on electrical steels, was proposed for realizing the core fabrication and the rotary transformer assembly. The results show that the rotary transformer can step down 400 V/50 Hz three-phase voltage to 13.15V in a Delta-wye connection and output 1.17kW power over an air-gap of 0.3mm with 95.94% overall efficiency. The proposed mechanical design enables the transformer to minimize the core loss and the manufacturing cost. Without using resonant inductive coupling, this transformer design simplifies the power supply for the motor, thereby decreasing the motor manufacturing and maintenance cost.

Le récepteur de chimiokine CXCR7 a été récemment identifié comme liant la chimiokine SDF-1, anciennement considérée comme ligand exclusif du récepteur CXCR4. Ces deux récepteurs sont exprimés majoritairement dans les mêmes types cellulaires et, ainsi, la découverte de CXCR7 incite à réévaluer les effets respectifs de SDF-1 sur CXCR4. Étant donné son rôle dans le cancer, CXCR4 est une cible de choix pour le développement de molécules thérapeutiques. Également, CXCR7 semble être impliqué dans la croissance tumorale. AMD3100, un antagoniste «sélectif» pour CXCR4, est maintenant commercialisé. Cet antagoniste a été identifié comme liant lui aussi CXCR7. De plus, sur CXCR7, l’AMD3100 agit comme agoniste puisqu’il induit le recrutement de la β-arrestine, à l’opposé de son effet sur. En revanche, AMD3100 n’induit pas le recrutement de la β-arrestine à CXCR4. Basé sur ces résultats, il est nécessaire de revoir la sélectivité d’autres antagonistes synthétiques de CXCR4. À l’aide de la technique de BRET (Résonance d’un transfert d’énergie par bioluminescence), nos résultats montrent que le Tc14012, un autre antagoniste synthétique de CXCR4, et structurellement distinct de l’AMD3100, interagit avec CXCR7. Contrairement à CXCR4, les deux antagonistes de CXCR4 agissent comme agonistes sur CXCR7 en induisant le recrutement de la β-arrestine. Nos résultats suggèrent que l’organisation spatiale du corps du récepteur serait responsable de cet effet opposé. En conclusion, AMD3100 et Tc14012 ne sont pas sélectifs pour CXCR4, puisqu’ils interagissent avec CXCR7. Lors du développement de nouvelles molécules synthétiques ciblant CXCR4, il serait alors nécessaire d’en évaluer leur sélectivité, et leurs effets en les testant aussi sur CXCR7. / ASBTRACT SDF-1 was at first thought to exclusively bind CXCR4, but it was subsequently found to also bind to the chemokine receptor CXCR7. CXCR4 is a promising target for drug development due to its role in cancer. AMD3100 is newly commercialised synthetic antagonist of CXCR4. This drug leads to massive release of hematopoietic stem cell into the peripheral blood. It was found that AMD3100 also binds to CXCR7 and acts as an agonist of β-arrestin recruitment to CXCR7. An antagonist of CXCR4 acts as an agonist on CXCR7. Prompted by this observation, we tested whether this might hold true for other CXCR4 antagonist. Tc14012, a peptidomimetic of T140, has been extensively described as a potent CXCR4 antagonist. We find that TC14012 also interacts on CXCR7. Like AMD3100, TC14012 alone induces β-arrestin recruitment to CXCR7. Thus, two structurally unrelated CXCR4 antagonists, AMD3100 and TC14012, are agonists of the CXCR7-arrestin pathway. This suggests distinct activation mechanisms of the arrestin pathway by CXCR4 and CXCR7. The results we obtained using a BRET (Bioluminescence Resonance Energy Transfer)-based arrestin recruitment assay, suggest that the CXCR7 receptor core is responsible for the recruitment of beta-arrestin in response to AMD3100 and TC14012. The finding that both AMD3100 and TC14012 do not only bind CXCR4, but also CXCR7, with opposite effects on arrestin recruitment, is important for the use of the compounds as tools to dissect SDF-1-mediated effects. This may be a general feature of synthetic ligands of the two receptors, with potential consequences for drug development. Key words: Chemokine receptor, CXCR4 and CXCR7, BRET, β-arrestin recruitement, TC14012, AMD3100 and SDF-1.

De nouveaux nano-objets anisotropes fluorescents sont obtenus par l’assemblage d’acènes spécifiquement conçus. Dans des cristaux, nano-rubans et nanoparticules anisotropes de 2,3-dialkyldiphenylanthracènes, les efficacités et la polarisation de l’émission bleue sont remarquables. La couleur de l’émission est accordée par le dopage avec des émetteurs verts et oranges (di- et tétra-phényltétracènes). La microscopie confocale de fluorescence permet d’étudier les cinétiques des états excités et des transferts d’énergie photo-induits, ainsi que la dispersion et les orientations des émetteurs. Pour la première fois, l’influence de la largeur de nano-rubans sur la cinétique d’annihilations triplet-triplet de tétracènes est mise en évidence. La microscopie révèle également le polymorphisme inhabituel d’un dérivé diéthynylphényl-anthracène. Ce travail ouvre des perspectives pour le développement et l’étude de processus fondamentaux de nano-matériaux luminescents. / New fluorescent anisotropic nano-objects are obtained by the assembly of specifically designed acenes. In crystals, nano-ribbons and anisotropic nanoparticles of 2,3-dialkyldiphenylanthracenes, the efficiencies and the polarization of the blue emission is remarkable. The color of the emission is tuned by doping with green and orange emitters (di-and tetra-phenyltetracenes). Confocal fluorescence microscopy is used to study the kinetics of excited states and photo-induced energy transfers, as well as the dispersion and orientation of the emitters. For the first time, the influence of the width of the nano-ribbons on the kinetics of tetracene triplet-triplet annihilations is highlighted. Microscopy also reveals the unusual polymorphism of a diethynylphenyl anthracene derivative. This work opens perspectives for the development and study of fundamental processes of luminescent nano-materials.