Development of Plasmonic Nanoplatforms for Diagnostics, Therapy, and Sensing

Recent advances in nanotechnology have led to the application of nanoparticles in a wide variety of fields. In the field of nanomedicine, there is great emphasis on combining diagnostic and therapeutic modalities into a single nanoparticle construct (theranostics). In particular, anisotropic nanoparticles have shown great potential for surface-enhanced Raman scattering (SERS) detection due to their unique optical properties. Gold nanostars are a type of anisotropic nanoparticle with one of the highest SERS enhancement factors in a non-aggregated state. By utilizing the distinct characteristics of gold nanostars, new plasmonic materials for diagnostics, therapy, and sensing can be synthesized. The work described herein is divided into two main themes. The first half presents a novel, theranostic nanoplatform that can be used for both SERS detection and photodynamic therapy (PDT). The second half involves the rational design of silver-coated gold nanostars for increasing SERS signal intensity and improving reproducibility and quantification in SERS measurements.

The theranostic nanoplatforms consist of Raman-labeled gold nanostars coated with a silica shell. Photosensitizer molecules for PDT can be loaded into the silica matrix, while retaining the SERS signal of the gold nanostar core. SERS detection and PDT are performed at different wavelengths, so there is no interference between the diagnostic and therapeutic modalities. Singlet oxygen generation (a measure of PDT effectiveness) was demonstrated from the drug-loaded nanocomposites. In vitro testing with breast cancer cells showed that the nanoplatform could be successfully used for PDT. When further conjugating the nanoplatform with a cell-penetrating peptide (CPP), efficacy of both SERS detection and PDT is enhanced.

The rational design of plasmonic nanoparticles for SERS sensing involved the synthesis of silver-coated gold nanostars. Investigation of the silver coating process revealed that preservation of the gold nanostar tips was necessary to achieve the increased SERS intensity. At the optimal amount of silver coating, the SERS intensity is increased by over an order of magnitude. It was determined that a majority of the increased SERS signal can be attributed to reducing the inner filter effect, as the silver coating process moves the extinction of the particles far away from the laser excitation line. To improve reproducibility and quantitative SERS detection, an internal standard was incorporated into the particles. By embedding a small-molecule dye between the gold and silver surfaces, SERS signal was obtained both from the internal dye and external analyte on the particle surface. By normalizing the external analyte signal to the internal reference signal, reproducibility and quantitative analysis are improved in a variety of experimental conditions.

Mechanochemistry for Active Materials and Devices

The coupling of mechanical stress fields in polymers to covalent chemistry (polymer mechanochemistry) has provided access to previously unattainable chemical reactions and polymer transformations. In the bulk, mechanochemical activation has been used as the basis for new classes of stress-responsive polymers that demonstrate stress/strain sensing, shear-induced intermolecular reactivity for molecular level remodeling and self-strengthening, and the release of acids and other small molecules that are potentially capable of triggering further chemical response. The potential utility of polymer mechanochemistry in functional materials is limited, however, by the fact that to date, all reported covalent activation in the bulk occurs in concert with plastic yield and deformation, so that the structure of the activated object is vastly different from its nascent form. Mechanochemically activated materials have thus been limited to “single use” demonstrations, rather than as multi-functional materials for structural and/or device applications. Here, we report that filled polydimethylsiloxane (PDMS) elastomers provide a robust elastic substrate into which mechanophores can be embedded and activated under conditions from which the sample regains its original shape and properties. Fabrication is straightforward and easily accessible, providing access for the first time to objects and devices that either release or reversibly activate chemical functionality over hundreds of loading cycles.

While the mechanically accelerated ring-opening reaction of spiropyran to merocyanine and associated color change provides a useful method by which to image the molecular scale stress/strain distribution within a polymer, the magnitude of the forces necessary for activation had yet to be quantified. Here, we report single molecule force spectroscopy studies of two spiropyran isomers. Ring opening on the timescale of tens of milliseconds is found to require forces of ~240 pN, well below that of previously characterized covalent mechanophores. The lower threshold force is a combination of a low force-free activation energy and the fact that the change in rate with force (activation length) of each isomer is greater than that inferred in other systems. Importantly, quantifying the magnitude of forces required to activate individual spiropyran-based force-probes enables the probe behave as a “scout” of molecular forces in materials; the observed behavior of which can be extrapolated to predict the reactivity of potential mechanophores within a given material and deformation.

We subsequently translated the design platform to existing dynamic soft technologies to fabricate the first mechanochemically responsive devices; first, by remotely inducing dielectric patterning of an elastic substrate to produce assorted fluorescent patterns in concert with topological changes; and second, by adopting a soft robotic platform to produce a color change from the strains inherent to pneumatically actuated robotic motion. Shown herein, covalent polymer mechanochemistry provides a viable mechanism to convert the same mechanical potential energy used for actuation into value-added, constructive covalent chemical responses. The color change associated with actuation suggests opportunities for not only new color changing or camouflaging strategies, but also the possibility for simultaneous activation of latent chemistry (e.g., release of small molecules, change in mechanical properties, activation of catalysts, etc.) in soft robots. In addition, mechanochromic stress mapping in a functional actuating device might provide a useful design and optimization tool, revealing spatial and temporal force evolution within the actuator in a way that might also be coupled to feedback loops that allow autonomous, self-regulation of activity.

In the future, both the specific material and the general approach should be useful in enriching the responsive functionality of soft elastomeric materials and devices. We anticipate the development of new mechanophores that, like the materials, are reversibly and repeatedly activated, expanding the capabilities of soft, active devices and further permitting dynamic control over chemical reactivity that is otherwise inaccessible, each in response to a single remote signal.

Integrated Housing Approach for Riyadh’s hot arid Climate: solutions from the desert vernacular

Thesis (Master's)--University of Washington, 2016-06

Tsunami characteristics along the Peru-Chile trench: analysis of the 2015 Mw8.3 Illapel, the 2014 Mw8.2 iquique and the 2010 Mw8.8 maule tsunamis in the near-field

Tsunamis occur quite frequently following large magnitude earthquakes along the Chilean coast. Most of these earthquakes occur along the Peru-Chile Trench, one of the most seismically active subduction zones of the world. This study aims to understand better the characteristics of the tsunamis triggered along the Peru-Chile Trench. We investigate the tsunamis induced by the Mw8.3 Illapel, the Mw8.2 Iquique and the Mw8.8 Maule Chilean earthquakes that happened on September 16th, 2015, April 1st, 2014 and February 27th, 2010, respectively. The study involves the relation between the co-seismic deformation and the tsunami generation, the near-field tsunami propagation, and the spectral analysis of the recorded tsunami signals in the near-field. We compare the tsunami characteristics to highlight the possible similarities between the three events and, therefore, attempt to distinguish the specific characteristics of the tsunamis occurring along the Peru-Chile Trench. We find that these three earthquakes present faults with important extensions beneath the continent which result in the generation of tsunamis with short wavelengths, relative to the fault widths involved, and with reduced initial potential energy. In addition, the presence of the Chilean continental margin, that includes the shelf of shallow bathymetry and the continental slope, constrains the tsunami propagation and the coastal impact. All these factors contribute to a concentrated local impact but can, on the other hand, reduce the far-field tsunami effects from earthquakes along Peru-Chile Trench.

Gait Regulation for Bipedal Locomotion

This work explores regulation of forward speed, step length, and slope walking for the passive-dynamic class of bipedal robots. Previously, an energy-shaping control for regulating forward speed has appeared in the literature; here we show that control to be a special case of a more general time-scaling control that allows for speed transitions in arbitrary time. As prior work has focused on potential energy shaping for fully actuated bipeds, we study in detail the shaping of kinetic energy for bipedal robots, giving special treatment to issues of underactuation. Drawing inspiration from features of human walking, an underactuated kinetic-shaping control is presented that provides efficient regulation of walking speed while adjusting step length. Previous results on energetic symmetries of bipedal walking are also extended, resulting in a control that allows regulation of speed and step length while walking on any slope. Finally we formalize the optimal gait regulation problem and propose a dynamic programming solution seeded with passive-dynamic limit cycles. Observations of the optimal solutions generated by this method reveal further similarities between passive dynamic walking and human locomotion and give insight into the structure of minimum-effort controls for walking.

Avaliação do potencial passível de conversão em energia elétrica das correntes na plataforma continental sul brasileira

O contínuo crescimento da população mundial aumenta a demanda e a competição por energia, colocando grande esforço sobre as fontes de energia não renováveis existentes. Devido a isso, políticas globais para geração de energias renováveis e menos poluentes estão sendo fortalecidas, além de promoverem o desenvolvimento de novas tecnologias. Várias formas de conversão de energia foram desenvolvidas no decorrer dos anos, com destaque para os conversores de energia das correntes a base de turbinas, que demonstram alta capacidade de conversão energética e já se encontram em funcionamento. O modelo tridimensional TELEMAC3D foi utilizado para a investigação dos processos hidrodinâmicos. Este modelo foi acoplado ao módulo de conversão de energia para as análises nos locais de maior viabilidade e conversão energética na Plataforma Continental do Sul do Brasil. A região de estudo demonstrou possuir duas regiões com alto potencial para a exploração da energias das correntes marinhas, entretanto a região mais viável para a instalação de conversores de corrente é a região norte delimitada entre o Farol da Conceição e o Farol da Solidão, podendo atingir potência média de 10kW=Dia, e alcançando valores integrados de 3:5MW=Ano. Através de uma análise da sazonalidade foram observados, durante a primavera os períodos mais energéticos em ambas as regiões estudadas. As maiores intensidades de conversão de energia foram estimadas com variabilidade temporal de 16 dias, demonstrando alta correlação com eventos associados à passagem de frentes meteorológicas na região. O sítio da região norte, com a presença de barreiras que representam a forma dos conversores, se destaca mantendo boa conversão durante os eventos de ótimo potencial energético. Esta melhora se deve ao efeito de intensificação do campo de correntes associado à presença da estrutura física que otimiza a eficiência do sítio. Não foram observadas diferenças significativas no padrão de variabilidade temporal das simulações estudadas, indicando que a presença das barreiras não induz grandes alterações no padrão temporal da conversão de energia nas escalas temporais analisadas neste trabalho. Os eventos de alta geração de energia foram relacionados a incidência de fortes ventos de quadrante sul e norte, indicando que pelo formato e disposição dos conversores, ventos de sudoeste e norte podem favorecer ótimos eventos de conversão de energia. As simulações dos sítios de conversão demonstraram alta capacidade de geração energética, com quatro eventos de extrema geração de energia. Entretanto, o sítio da região norte demonstrou eficiência superior a 59,39 GWh ao ano, equivalendo a 0.22% do consumo energético do estado do Rio Grande do Sul no ano de 2010.

Performance Energética no contexto do sistema LEED

Com o aumento constante de procura de recursos naturais por parte dos vários setores da sociedade é urgente encontrar soluções para reduzir o seu consumo sem se travar a expansão demográfica que se tem vindo a sentir nos grandes centros urbanos. É através da implementação de medidas de sustentabilidade e pelo aumento da eficiência de utilização desses recursos que se tem vindo a combater esta tendência cada vez maior de consumismo global, sendo isto apenas possível com a implementação de ferramentas tecnológicas avançadas que permitem estabelecer limites ao considerado eficiente e premiando, em termos financeiros e de imagem de marketing, as entidades que o alcancem. O LEED é um sistema de certificação de sustentabilidade voluntário de edifícios residenciais e comerciais que estabelece métricas de comparação de parâmetros indicadores de consumos energéticos, hídricos e de materiais em todo o ciclo de vida do edifício e que tem vindo a ganhar destaque em crescendo a nível mundial. Esta dissertação teve como objetivo comparar a performance de consumo energético no âmbito do sistema LEED com a do sistema de certificação energética de edifícios nacional (SCE) de um grande edifício de serviços, estabelecendo um paralelismo de semelhanças e diferenças entre os dois e de avaliar os efeitos de potenciais medidas de eficiência energética e seus efeitos nas classificações de mérito obtidas em cada sistema. Os resultados obtidos na simulação que permitiu avaliar a performance foi muito satisfatório, tendo sido aproveitado pela empresa para efeitos de certificação LEED do edifício em estudo.

Asymptotic analysis of combined breather-kink modes in a Fermi-Pasta-Ulam chain

We find approximations to travelling breather solutions of the one-dimensional Fermi-Pasta-Ulam (FPU) lattice. Both bright breather and dark breather solutions are found. We find that the existence of localised (bright) solutions depends upon the coefficients of cubic and quartic terms of the potential energy, generalising an earlier inequality derived by James [CR Acad Sci Paris 332, 581, (2001)]. We use the method of multiple scales to reduce the equations of motion for the lattice to a nonlinear Schr{\"o}dinger equation at leading order and hence construct an asymptotic form for the breather. We show that in the absence of a cubic potential energy term, the lattice supports combined breathing-kink waveforms. The amplitude of breathing-kinks can be arbitrarily small, as opposed to traditional monotone kinks, which have a nonzero minimum amplitude in such systems. We also present numerical simulations of the lattice, verifying the shape and velocity of the travelling waveforms, and confirming the long-lived nature of all such modes.

Numerical Simulations of Fog Events in Southern Portugal

This work aims at improving the knowledge on fog formation and its evolution in the Alentejo region (Portugal). For this purpose, brief regional fog climatology, essentially based on information from the Beja Air Base meteorological station, was produced and several numerical high resolution simulations were performed using the Meso-NH. The ECOCLIMAP database used to generate the model physiography was improved to include the Alqueva reservoir (~250 km2), filled in 2003. The model results were compared with surface and satellite observations, showing good agreement in terms of fog occurrence and persistence. Various forcing mechanisms for formation, development, and dissipation of fog were identified, confirming the influence of two small mountains that block the moist air from the Atlantic Ocean, preventing the fog from reaching innermost regions. The introduction of the Alqueva large reservoir induces changes in the landscape and environment. The effects of the water vapour addition and of the changes in mass and energy surface fluxes on fog formation and evolution were studied. It was found that the reservoir may have a direct impact on fog formation over the lake and its vicinity. Depending on the large scale meteorological conditions, their influence can be both positive and negative, in terms of spatial coverage and temporal persistence.

Energy window effect in chemisorption of C36 on diamond (001)-(/2×1) surface

In this paper, the collision of a C36, with D6h symmetry, on diamond (001)-(/2×1) surface was investigated using molecular dynamics (MD) simulation based on the semi-empirical Brenner potential. The incident kinetic energy of the C36 ranges from 20 to 150 eV per cluster. The collision dynamics was investigated as a function of impact energy Ein. The C36 cluster was first impacted towards the center of two dimers with a fixed orientation. It was found that when Ein was lower than 30 eV, C36 bounces off the surface without breaking up. Increasing Ein to 30-45 eV, bonds were formed between C36 and surface dimer atoms, and the adsorbed C36 retained its original free-cluster structure. Around 50-60 eV, the C36 rebounded from the surface with cage defects. Above 70 eV, fragmentation both in the cluster and on the surface was observed. Our simulation supported the experimental findings that during low-energy cluster beam deposition small fullerenes could keep their original structure after adsorption (i.e. the memory effect), if Ein is within a certain range. Furthermore, we found that the energy threshold for chemisorption is sensitive to the orientation of the incident C36 and its impact position on the asymmetric surface.

Effect of Surface Potential Barrier on the Electron Energy Distribution of NEA Photocathodes

By calculating the energy distribution of electrons reaching the photocathode surface and solving the Schrodinger equation that describes the behavior of an electron tunneling through the surface potential barrier,we obtain an equation to calculate the emitted electron energy distribution of transmission-mode NEA GaAs photocathodes. Accord- ing to the equation,we study the effect of cathode surface potential barrier on the electron energy distribution and find a significant effect of the barrier-Ⅰ thickness or end height,especially the thickness,on the quantum efficiency of the cath- ode. Barrier Ⅱ has an effect on the electron energy spread, and an increase in the vacuum level will lead to a narrower electron energy spread while sacrificing a certain amount of cathode quantum efficiency. The equation is also used to fit the measured electron energy distribution curve of the transmission-mode cathode and the parameters of the surface barri- er are obtained from the fitting. The theoretical curve is in good agreement with the experimental curve.

“Acid-spike” effect in spurs/tracks of the low/high linear energy transfer radiolysis of water : potential implications for radiobiology and nuclear industry

Résumé : Les ions hydronium (H3O + ) sont formés, à temps courts, dans les grappes ou le long des trajectoires de la radiolyse de l'eau par des rayonnements ionisants à faible transfert d’énergie linéaire (TEL) ou à TEL élevé. Cette formation in situ de H3O + rend la région des grappes/trajectoires du rayonnement temporairement plus acide que le milieu environnant. Bien que des preuves expérimentales de l’acidité d’une grappe aient déjà été signalées, il n'y a que des informations fragmentaires quant à son ampleur et sa dépendance en temps. Dans ce travail, nous déterminons les concentrations en H3O + et les valeurs de pH correspondantes en fonction du temps à partir des rendements de H3O + calculés à l’aide de simulations Monte Carlo de la chimie intervenant dans les trajectoires. Quatre ions incidents de différents TEL ont été sélectionnés et deux modèles de grappe/trajectoire ont été utilisés : 1) un modèle de grappe isolée "sphérique" (faible TEL) et 2) un modèle de trajectoire "cylindrique" (TEL élevé). Dans tous les cas étudiés, un effet de pH acide brusque transitoire, que nous appelons un effet de "pic acide", est observé immédiatement après l’irradiation. Cet effet ne semble pas avoir été exploré dans l'eau ou un milieu cellulaire soumis à un rayonnement ionisant, en particulier à haut TEL. À cet égard, ce travail soulève des questions sur les implications possibles de cet effet en radiobiologie, dont certaines sont évoquées brièvement. Nos calculs ont ensuite été étendus à l’étude de l'influence de la température, de 25 à 350 °C, sur la formation in situ d’ions H3O + et l’effet de pic acide qui intervient à temps courts lors de la radiolyse de l’eau à faible TEL. Les résultats montrent une augmentation marquée de la réponse de pic acide à hautes températures. Comme de nombreux processus intervenant dans le cœur d’un réacteur nucléaire refroidi à l'eau dépendent de façon critique du pH, la question ici est de savoir si ces fortes variations d’acidité, même si elles sont hautement localisées et transitoires, contribuent à la corrosion et l’endommagement des matériaux.