Polymer nanoparticles : their functionalization for biomedical applications and dynamics near an electrode

In this work, a method for the functionalization of biocompatible, poly(lactic acid)-based nanoparticles with charged moieties or fluorescent labels is presented. Therefore, a miniemulsion solvent evaporation procedure is used in which prepolymerized poly(L-lactic acid) is used together with a previously synthesized copolymer of methacrylic acid or a polymerizable dye, respectively, and an oligo(lactic acid) macromonomer. Alternatively, the copolymerization has been carried out in one step with the miniemulsion solvent evaporation. The increased stability in salty solutions of the carboxyl-modified nanoparticles compared to nanoparticles consisting of poly(lactic acid) only has been shown in light scattering experiments. The properties of the nanoparticles that were prepared with the separately synthesized copolymer were almost identical to those in which the copolymerization and particle fabrication were carried out simultaneously. During the characterization of the fluorescently labeled nanoparticles, the focus was on the stable bonding between the fluorescent dye and the rest of the polymer chain to ensure that none of it is released from the particles, even after longer storage time or during lengthy experiments. In a fluorescence correlation spectroscopy experiment, it could be shown that even after two weeks, no dye has been released into the solvent. Besides biomedical research for which the above described, functionalized nanoparticles were optimized, nanoparticles also play a role in coating technology. One possibility to fabricate coatings is the electrophoretic deposition of particles. In this process, the mobility of nanoparticles near electrode interfaces plays a crucial role. In this thesis, the nanoparticle mobility has been investigated with resonance enhanced dynamic light scattering (REDLS). A new setup has been developed in which the evanescent electromagnetic eld of a surface plasmon that propagates along the gold-sample interface has been used as incident beam for the dynamic light scattering experiment. The gold layer that is necessary for the excitation of the plasmon doubles as an electrode. Due to the penetration depth of the surface plasmon into the sample layer that is limited to ca. 200 nm, insights on the voltage- and frequency dependent mobility of the nanoparticles near the electrode could be gained. Additionally, simultaneous measurements at four different scattering angles can be carried out with this setup, therefore the investigation of samples undergoing changes is feasible. The results were discussed in context with the mechanisms of electrophoretic deposition.

Rapid restoration of microcirculatory blood flow with hyperviscous and hyperoncotic solutions lowers the transfusion trigger in resuscitation from hemorrhagic shock

Resuscitation from hemorrhagic shock relies on fluid retransfusion. However, the optimal properties of the fluid have not been established. The aim of the present study was to test the influence of the concentration of hydroxyethyl starch (HES) solution on plasma viscosity and colloid osmotic pressure (COP), systemic and microcirculatory recovery, and oxygen delivery and consumption after resuscitation, which were assessed in the hamster chamber window preparation by intravital microscopy. Awake hamsters were subjected to 50% hemorrhage and were resuscitated with 25% of the estimated blood volume with 5%, 10%, or 20% HES solution. The increase in concentration led to an increase in COP (from 20 to 70 and 194 mmHg) and viscosity (from 1.7 to 3.8 and 14.4 cP). Cardiac index and microcirculatory and metabolic recovery were improved with HES 10% and 20% when compared with 5% HES. Oxygen delivery and consumption in the dorsal skinfold chamber was more than doubled with HES 10% and 20% when compared with HES 5%. This was attributed to the beneficial effect of restored or increased plasma COP and plasma viscosity as obtained with HES 10% and 20%, leading to improved microcirculatory blood flow values early in the resuscitation period. The increase in COP led to an increase in blood volume as shown by a reduction in hematocrit. Mean arterial pressure was significantly improved in animals receiving 10% and 20% solutions. In conclusion, the present results show that the increase in the concentration of HES, leading to hyperoncotic and hyperviscous solutions, is beneficial for resuscitation from hemorrhagic shock because normalization of COP and viscosity led to a rapid recovery of microcirculatory parameters.

Sediment yield reduction in an agricultural watershed

With proper application of Best Management Practices (BMPs), the impact from the sediment to the water bodies could be minimized. However, finding the optimal allocation of BMP can be difficult, since there are numerous possible options. Also, economics plays an important role in BMP affordability and, therefore, the number of BMPs able to be placed in a given budget year. In this study, two methodologies are presented to determine the optimal cost-effective BMP allocation, by coupling a watershed-level model, Soil and Water Assessment Tool (SWAT), with two different methods, targeting and a multi-objective genetic algorithm (Non-dominated Sorting Genetic Algorithm II, NSGA-II). For demonstration, these two methodologies were applied to an agriculture-dominant watershed located in Lower Michigan to find the optimal allocation of filter strips and grassed waterways. For targeting, three different criteria were investigated for sediment yield minimization, during the process of which it was found that the grassed waterways near the watershed outlet reduced the watershed outlet sediment yield the most under this study condition, and cost minimization was also included as a second objective during the cost-effective BMP allocation selection. NSGA-II was used to find the optimal BMP allocation for both sediment yield reduction and cost minimization. By comparing the results and computational time of both methodologies, targeting was determined to be a better method for finding optimal cost-effective BMP allocation under this study condition, since it provided more than 13 times the amount of solutions with better fitness for the objective functions while using less than one eighth of the SWAT computational time than the NSGA-II with 150 generations did.

Physical modeling of air injection as a scour remediation technique near gated weir stilling basins

The South Florida Water Management District (SFWMD) manages and operates numerous water control structures that are subject to scour. In an effort to reduce scour downstream of these gated structures, laboratory experiments were performed to investigate the effect of active air-injection downstream of the terminal structure of a gated spillway on the depth of the scour hole. A literature review involving similar research revealed significant variables such as the ratio of headwater-to-tailwater depths, the diffuser angle, sediment uniformity, and the ratio of air-to-water volumetric discharge values. The experimental design was based on the analysis of several of these non-dimensional parameters. Bed scouring at stilling basins downstream of gated spillways has been identified as posing a serious risk to the spillway’s structural stability. Although this type of scour has been studied in the past, it continues to represent a real threat to water control structures and requires additional attention. A hydraulic scour channel comprised of a head tank, flow straightening section, gated spillway, stilling basin, scour section, sediment trap, and tail-tank was used to further this analysis. Experiments were performed in a laboratory channel consisting of a 1:30 scale model of the SFWMD S65E spillway structure. To ascertain the feasibility of air injection for scour reduction a proof-of-concept study was performed. Experiments were conducted without air entrainment and with high, medium, and low air entrainment rates for high and low headwater conditions. For the cases with no air entrainment it was found that there was excessive scour downstream of the structure due to a downward roller formed upon exiting the downstream sill of the stilling basin. When air was introduced vertically just downstream of, and at the same level as, the stilling basin sill, it was found that air entrainment does reduce scour depth by up to 58% depending on the air flow rate, but shifts the deepest scour location to the sides of the channel bed instead of the center. Various hydraulic flow conditions were tested without air injection to verify which scenario caused more scour. That scenario, uncontrolled free, in which water does not contact the gate and the water elevation in the stilling basin is lower than the spillway crest, would be used for the remainder of experiments testing air injection. Various air flow rates, diffuser elevations, air hole diameters, air hole spacings, diffuser angles and widths were tested in over 120 experiments. Optimal parameters include air injection at a rate that results in a water-to-air ratio of 0.28, air holes 1.016mm in diameter the entire width of the stilling basin, and a vertically orientated injection pattern. Detailed flow measurements were collected for one case using air injection and one without. An identical flow scenario was used for each experiment, namely that of a high flow rate and upstream headwater depth and a low tailwater depth. Equilibrium bed scour and velocity measurements were taken using an Acoustic Doppler Velocimeter at nearly 3000 points. Velocity data was used to construct a vector plot in order to identify which flow components contribute to the scour hole. Additionally, turbulence parameters were calculated in an effort to help understand why air-injection reduced bed scour. Turbulence intensities, normalized mean flow, normalized kinetic energy, and anisotropy of turbulence plots were constructed. A clear trend emerged that showed air-injection reduces turbulence near the bed and therefore reduces scour potential.

Numerical solution of optimal control problems with constant control delays

We investigate a class of optimal control problems that exhibit constant exogenously given delays in the control in the equation of motion of the differential states. Therefore, we formulate an exemplary optimal control problem with one stock and one control variable and review some analytic properties of an optimal solution. However, analytical considerations are quite limited in case of delayed optimal control problems. In order to overcome these limits, we reformulate the problem and apply direct numerical methods to calculate approximate solutions that give a better understanding of this class of optimization problems. In particular, we present two possibilities to reformulate the delayed optimal control problem into an instantaneous optimal control problem and show how these can be solved numerically with a stateof- the-art direct method by applying Bock’s direct multiple shooting algorithm. We further demonstrate the strength of our approach by two economic examples.

Privacy-Preserving Optimal Meeting Location Determination on Mobile Devices

Equipped with state-of-the-art smartphones and mobile devices, today's highly interconnected urban population is increasingly dependent on these gadgets to organize and plan their daily lives. These applications often rely on current (or preferred) locations of individual users or a group of users to provide the desired service, which jeopardizes their privacy; users do not necessarily want to reveal their current (or preferred) locations to the service provider or to other, possibly untrusted, users. In this paper, we propose privacy-preserving algorithms for determining an optimal meeting location for a group of users. We perform a thorough privacy evaluation by formally quantifying privacy-loss of the proposed approaches. In order to study the performance of our algorithms in a real deployment, we implement and test their execution efficiency on Nokia smartphones. By means of a targeted user-study, we attempt to get an insight into the privacy-awareness of users in location-based services and the usability of the proposed solutions.

The Optimal Capital Structure of Banks: Balancing Deposit Insurance, Capital Requirements and Tax-Advantaged Debt

The capital structure and regulation of financial intermediaries is an important topic for practitioners, regulators and academic researchers. In general, theory predicts that firms choose their capital structures by balancing the benefits of debt (e.g., tax and agency benefits) against its costs (e.g., bankruptcy costs). However, when traditional corporate finance models have been applied to insured financial institutions, the results have generally predicted corner solutions (all equity or all debt) to the capital structure problem. This paper studies the impact and interaction of deposit insurance, capital requirements and tax benefits on a bankÇs choice of optimal capital structure. Using a contingent claims model to value the firm and its associated claims, we find that there exists an interior optimal capital ratio in the presence of deposit insurance, taxes and a minimum fixed capital standard. Banks voluntarily choose to maintain capital in excess of the minimum required in order to balance the risks of insolvency (especially the loss of future tax benefits) against the benefits of additional debt. Because we derive a closed- form solution, our model provides useful insights on several current policy debates including revisions to the regulatory framework for GSEs, tax policy in general and the tax exemption for credit unions.

Desarrollo de estructuras nanofotonicas de campo cercano para intensificacion localizada de luz en celulas solares de banda intermedia - Near-field nanophotonic structures for localized light enhancement in intermediate band solar cells

This doctoral thesis explores some of the possibilities that near-field optics can bring to photovoltaics, and in particular to quantum-dot intermediate band solar cells (QD-IBSCs). Our main focus is the analytical optimization of the electric field distribution produced in the vicinity of single scattering particles, in order to produce the highest possible absorption enhancement in the photovoltaic medium in their surroundings. Near-field scattering structures have also been fabricated in laboratory, allowing the application of the previously studied theoretical concepts to real devices. We start by looking into the electrostatic scattering regime, which is only applicable to sub-wavelength sized particles. In this regime it was found that metallic nano-spheroids can produce absorption enhancements of about two orders of magnitude on the material in their vicinity, due to their strong plasmonic resonance. The frequency of such resonance can be tuned with the shape of the particles, allowing us to match it with the optimal transition energies of the intermediate band material. Since these metallic nanoparticles (MNPs) are to be inserted inside the cell photovoltaic medium, they should be coated by a thin insulating layer to prevent electron-hole recombination at their surface. This analysis is then generalized, using an analytical separation-of-variables method implemented in Mathematica7.0, to compute scattering by spheroids of any size and material. This code allowed the study of the scattering properties of wavelengthsized particles (mesoscopic regime), and it was verified that in this regime dielectric spheroids perform better than metallic. The light intensity scattered from such dielectric spheroids can have more than two orders of magnitude than the incident intensity, and the focal region in front of the particle can be shaped in several ways by changing the particle geometry and/or material. Experimental work was also performed in this PhD to implement in practice the concepts studied in the analysis of sub-wavelength MNPs. A wet-coating method was developed to self-assemble regular arrays of colloidal MNPs on the surface of several materials, such as silicon wafers, amorphous silicon films, gallium arsenide and glass. A series of thermal and chemical tests have been performed showing what treatments the nanoparticles can withstand for their embedment in a photovoltaic medium. MNPs arrays are then inserted in an amorphous silicon medium to study the effect of their plasmonic near-field enhancement on the absorption spectrum of the material. The self-assembled arrays of MNPs constructed in these experiments inspired a new strategy for fabricating IBSCs using colloidal quantum dots (CQDs). Such CQDs can be deposited in self-assembled monolayers, using procedures similar to those developed for the patterning of colloidal MNPs. The use of CQDs to form the intermediate band presents several important practical and physical advantages relative to the conventional dots epitaxially grown by the Stranski-Krastanov method. Besides, this provides a fast and inexpensive method for patterning binary arrays of QDs and MNPs, envisioned in the theoretical part of this thesis, in which the MNPs act as antennas focusing the light in the QDs and therefore boosting their absorption

Characterization cement pastes degraded in lanoratory solutions and physiochemical parameters employed for modeling the process

Previously degradation studies carried out, over a number of different mortars by the research team, have shown that observed degradation does not exclusively depend on the solution equilibrium pH, nor the aggressive anions relative solubility. In our tests no reason was found that could allow us to explain, why same solubility anions with a lower pH are less aggressive than others. The aim of this paper is to study cement pastes behavior in aggressive environments. As observed in previous research, this cement pastes behaviors are not easily explained only taking into account only usual parameters, pH, solubility etc. Consequently the paper is about studying if solution physicochemical characteristics are more important in certain environments than specific pH values. The paper tries to obtain a degradation model, which starting from solution physicochemical parameters allows us to interpret the different behaviors shown by different composition cements. To that end, the rates of degradation of the solid phases were computed for each considered environment. Three cement have been studied: CEM I 42.5R/SR, CEM II/A-V 42.5R and CEM IV/B-(P-V) 32.5 N. The pastes have been exposed to five environments: sodium acetate/acetic acid 0.35 M, sodium sulfate solution 0.17 M, a solution representing natural water, saturated calcium hydroxide solution and laboratory environment. The attack mechanism was meant to be unidirectional, in order to achieve so; all sides of cylinders were sealed except from the attacked surface. The cylinders were taking out of the exposition environments after 2, 4, 7, 14, 30, 58 and 90 days. Both aggressive solution variations in solid phases and in different depths have been characterized. To each age and depth the calcium, magnesium and iron contents have been analyzed. Hydrated phases evolution studied, using thermal analysis, and crystalline compound changes, using X ray diffraction have been also analyzed. Sodium sulphate and water solutions stabilize an outer pH near to 8 in short time, however the stability of the most pH dependent phases is not the same. Although having similar pH and existing the possibility of forming a plaster layer near to the calcium leaching surface, this stability is greater than other sulphate solutions. Stability variations of solids formed by inverse diffusion, determine the rate of degradation.

Propagation Mechanism modeling in the Near-Region of Arbitrary Cross-Sectional Tunnels.

Along with the increase of the use of working frequencies in advanced radio communication systems, the near-region inside tunnels lengthens considerably and even occupies the whole propagation cell or the entire length of some short tunnels. This paper analytically models the propagation mechanisms and their dividing point in the near-region of arbitrary cross-sectional tunnels for the first time. To begin with, the propagation losses owing to the free space mechanism and the multimode waveguide mechanism are modeled, respectively. Then, by conjunctively employing the propagation theory and the three-dimensional solid geometry, the paper presents a general model for the dividing point between two propagation mechanisms. It is worthy to mention that this model can be applied in arbitrary cross-sectional tunnels. Furthermore, the general dividing point model is specified in rectangular, circular, and arched tunnels, respectively. Five groups of measurements are used to justify the model in different tunnels at different frequencies. Finally, in order to facilitate the use of the model, simplified analytical solutions for the dividing point in five specific application situations are derived. The results in this paper could help deepen the insight into the propagation mechanisms in tunnels.

Análisis de la influencia de distintos diseños de paraguas de micropilotes, pantalla de micropilotes, paraguas de jet grouting y pantallas de jet grouting en los asientos en superficie durante la ejecución de túneles perforados superficialmente

Ya en el informe acerca del estado de la tecnología en la excavación profunda y en la construcción de túneles en terreno duro presentado en la 7ª Conferencia en Mecánica de Suelos e Ingeniería de la Cimentación, Peck (1969) introdujo los tres temas a ser tenidos en cuenta para el diseño de túneles en terrenos blandos: o Estabilidad de la cavidad durante la construcción, con particular atención a la estabilidad del frente del túnel; o Evaluación de los movimientos del terreno inducidos por la construcción del túnel y de la incidencia de los trabajos subterráneos a poca profundidad sobre los asentamientos en superficie; o Diseño del sistema de sostenimiento del túnel a instalar para asegurar la estabilidad de la estructura a corto y largo plazo. Esta Tesis se centra en los problemas señalados en el segundo de los puntos, analizando distintas soluciones habitualmente proyectadas para reducir los movimientos inducidos por la excavación de los túneles. El objeto de la Tesis es el análisis de la influencia de distintos diseños de paraguas de micropilotes, pantalla de micropilotes, paraguas de jet grouting y pantallas de jet grouting en los asientos en superficie durante la ejecución de túneles ejecutados a poca profundidad, con objeto de buscar el diseño que optimice los medios empleados para una determinada reducción de asientos. Para ello se establecen unas premisas para los proyectistas con objeto de conocer a priori cuales son los tratamientos más eficientes (de los propuestos en la Tesis) para la reducción de asientos en superficie cuando se ha de proyectar un túnel, de tal manera que pueda tener datos cualitativos y algunos cuantitativos sobre los diseños más óptimos, utilizando para ello un programa de elementos finitos de última generación que permite realizara la simulación tensodeformación del terreno mediante el modelo de suelo con endurecimiento (Hardening Soil Small model), que es una variante elastoplástica del modelo hiperbólico, similar al Hardening Soil Model. Además, este modelo incorpora una relación entre deformación y el modulo de rigidez, simulando el diferente comportamiento del suelo para pequeñas deformaciones (por ejemplo vibraciones con deformaciones por debajo de 10-5 y grandes deformaciones (deformaciones > 10-3). Para la realización de la Tesis se han elegido cinco secciones de túnel, dos correspondiente a secciones tipo de túnel ejecutado con tuneladora y tres secciones ejecutados mediante convencionales (dos correspondientes a secciones que han utilizado el método Belga y una que ha utilizado el NATM). Para conseguir los objetivos marcados, primeramente se ha analizado mediante una correlación entre modelos tridimensionales y bidimensionales el valor de relajación usado en estos últimos, y ver su variación al cambio de parámetros como la sección del túnel, la cobertera, el procedimiento constructivo, longitud de pase (métodos convencionales) o presión del frente (tuneladora) y las características geotécnicas de los materiales donde se ejecuta el túnel. Posteriormente se ha analizado que diseño de pantalla de protección tiene mejor eficacia respecto a la reducción de asientos, variando distintos parámetros de las características de la misma, como son el empotramiento, el tipo de micropilotes o pilote, la influencia del arriostramiento de las pantallas de protección en cabeza, la inclinación de la pantalla, la separación de la pantalla al eje del túnel y la disposición en doble fila de la pantalla de pantalla proyectada. Para finalizar el estudio de la efectividad de pantalla de protección para la reducción de asiento, se estudiará la influencia de la sobrecarga cercanas (simulación de edificios) tiene en la efectividad de la pantalla proyectada (desde el punto de vista de reducción de movimientos en superficie). Con objeto de poder comparar la efectividad de la pantalla de micropilotes respecto a la ejecución de un paraguas de micropilotes se ha analizado distintos diseños de paraguas, comparando el movimiento obtenido con el obtenido para el caso de pantalla de micropilotes, comparando ambos resultados con los medidos en obras ya ejecutadas. En otro apartado se ha realizado una comparación entre tratamientos similar, comparándolos en este caso con un paraguas de jet grouting y pantallas de jet grouting. Los resultados obtenidos se han con valores de asientos medidos en distintas obras ya ejecutadas y cuyas secciones se corresponden a los empleados en los modelos numéricos. Since the report on the state of technology in deep excavation and tunnelling in hard ground presented at the 7th Conference on Soil Mechanics and Foundation Engineering, Peck (1969) introduced the three issues to be taken into account for the design of tunnels in soft ground: o Cavity Stability during construction, with particular attention to the stability of the tunnel face; o Evaluation of ground movements induced by tunnelling and the effect of shallow underground workings on surface settlement; o Design of the tunnel support system to be installed to ensure short and long term stability of the structure. This thesis focuses on the issues identified in the second point, usually analysing different solutions designed to reduce the movements induced by tunnelling. The aim of the thesis is to analyse the influence of different micropile forepole umbrellas, micropile walls, jet grouting umbrellas and jet grouting wall designs on surface settlements during near surface tunnelling in order to use the most optimal technique to achieve a determined reduction in settlement. This will establish some criteria for designers to know a priori which methods are most effective (of those proposed in the thesis) to reduce surface settlements in tunnel design, so that it is possible to have qualitative and some quantitative data on the optimal designs, using the latest finite element modelling software that allows simulation of the ground’s infinitesimal strain behaviour using the Hardening Soil Small Model, which is a variation on the elasto-plastic hyperbolic model, similar to Hardening Soil model. In addition, this model incorporates a relationship between strain and the rigidity modulus, simulating different soil behaviour for small deformations (eg deformation vibrations below 10-5 and large deformations (deformations > 10-3). For the purpose of this thesis five tunnel sections have been chosen, two sections corresponding to TBM tunnels and three sections undertaken by conventional means (two sections corresponding to the Belgian method and one corresponding to the NATM). To achieve the objectives outlined, a correlation analysis of the relaxation values used in the 2D and 3D models was undertaken to verify them against parameters such as the tunnel cross-section, the depth of the tunnel, the construction method, the length of step (conventional method) or face pressure (TBM) and the geotechnical characteristics of the ground where the tunnel is constructed. Following this, the diaphragm wall design with the greatest efficiency regarding settlement reduction was analysed, varying parameters such as the toe depth, type of micropiles or piles, the influence of bracing of the head protection diaphragm walls, the inclination of the diaphragm wall, the separation between the diaphragm wall and the tunnel axis and the double diaphragm wall design arrangement. In order to complete the study into the effectiveness of protective diaphragm walls ofn the reduction of settlements, the influence of nearby imposed loads (simulating buildings) on the effectiveness of the designed diaphragm walls (from the point of view of reducing surface movements) will be studied. In order to compare the effectiveness of micropile diaphragm walls regarding the installation of micropile forepole umbrellas, different designs of these forepole umbrellas have been analysed comparing the movement obtained with that obtained for micropiled diaphragm walls, comparing both results with those measured from similar completed projects. In another section, a comparison between similar treatments has been completed, comparing the treatments with a forepole umbrella by jet grouting and jet grouting walls. The results obtained compared with settlement values measured in various projects already completed and whose sections correspond to those used in the numerical models.

Low-Dimensional Modelling for optimal streaks in the blasius boundary layer

This paper is concerned with the low dimensional structure of optimal streaks in the Blasius boundary layer. Optimal streaks are well known to exhibit an approximate self-similarity, namely the streamwise velocity re-scaled with their maximum remains almost independent of both the spanwise wavenumber and the streamwise coordinate. However, the reason of this self-similar behavior is still unexplained as well as unexploited. After revisiting the structure of the streaks near the leading edge singularity, two additional approximately self-similar relations involving the velocity components and their wall normal derivatives are identified. Based on these properties, we derive a low dimensional model with two degrees of freedom. The comparison with the results obtained from the linearized boundary layer equations shows that this model is consistent and provide good approximations.