Solid-state reference and ion-selective electrodes : towards portable potentiometric sensing

Potentiometric sensors are very attractive tools for chemical analysis because of their simplicity, low power consumption and low cost. They are extensively used in clinical diagnostics and in environmental monitoring. Modern applications of both fields require improvements in the conventional construction and in the performance of the potentiometric sensors, as the trends are towards portable, on-site diagnostics and autonomous sensing in remote locations. The aim of this PhD work was to improve some of the sensor properties that currently hamper the implementation of the potentiometric sensors in modern applications. The first part of the work was concentrated on the development of a solid-state reference electrode (RE) compatible with already existing solid-contact ion-selective electrodes (ISE), both of which are needed for all-solid-state potentiometric sensing systems. A poly(vinyl chloride) membrane doped with a moderately lipophilic salt, tetrabutylammonium-tetrabutylborate (TBA-TBB), was found to show a satisfactory stability of potential in sample solutions with different concentrations. Its response time was nevertheless slow, as it required several minutes to reach the equilibrium. The TBA-TBB membrane RE worked well together with solid-state ISEs in several different situations and on different substrates enabling a miniature design. Solid contacts (SC) that mediate the ion-to-electron transduction are crucial components of well-functioning potentiometric sensors. This transduction process converting the ionic conduction of an ion-selective membrane to the electronic conduction in the circuit was studied with the help of electrochemical impedance spectroscopy (EIS). The solid contacts studied were (i) the conducting polymer (CP) poly(3,4-ethylienedioxythiophene) (PEDOT) and (ii) a carbon cloth having a high surface area. The PEDOT films were doped with a large immobile anion poly(styrene sulfonate) (PSS-) or with a small mobile anion Cl-. As could be expected, the studied PEDOT solid-contact mediated the ion-toelectron transduction more efficiently than the bare glassy carbon substrate, onto which they were electropolymerized, while the impedance of the PEDOT films depended on the mobility of the doping ion and on the ions in the electrolyte. The carbon cloth was found to be an even more effective ion-to-electron transducer than the PEDOT films and it also proved to work as a combined electrical conductor and solid contact when covered with an ion-selective membrane or with a TBA-TBB-based reference membrane. The last part of the work was focused on improving the reproducibility and the potential stability of the SC-ISEs, a problem that culminates to the stability of the standard potential E°. It was proven that the E° of a SC-ISE with a conducting polymer as a solid contact could be adjusted by reducing or oxidizing the CP solid contact by applying current pulses or a potential to it, as the redox state of the CP solid-contact influences the overall potential of the ISE. The slope and thus the analytical performance of the SC-ISEs were retained despite the adjustment of the E°. The shortcircuiting of the SC-ISE with a conventional large-capacitance RE was found to be a feasible instrument-free method to control the E°. With this method, the driving force for the oxidation/reduction of the CP was the potential difference between the RE and the SC-ISE, and the position of the adjusted potential could be controlled by choosing a suitable concentration for the short-circuiting electrolyte. The piece-to-piece reproducibility of the adjusted potential was promising, and the day-today reproducibility for a specific sensor was excellent. The instrumentfree approach to control the E° is very attractive considering practical applications.

Prodrug strategies of antiviral nucleotides: Studies on enzymatically and thermally removable phosphate protecting groups

Antiviral nucleosides are compounds that are used against viruses, such as human immunodeficiency virus (HIV) and hepatitis C virus (HCV). To act as therapeutic agent, the antiviral nucleoside needs to be phosphorylated to nucleotide in the body in three consecutive phosphorylation steps by cellular or viral enzymes. The first phosphorylation to the nucleoside monophosphate is often inefficient and leads to poor antiviral activity. The antiviral efficacy can be improved by applying a prodrug strategy and delivering the antiviral nucleoside directly as its monophosphate. In prodrug strategies of antiviral nucleotides, the negative charges on the phosphate moiety are temporarily masked with protecting groups. Once inside the cell, the protecting groups are removed by enzymatic or chemical processes. Many prodrug strategies apply biodegradable protecting groups, the removal of which is triggered by esterase enzymes. Several studies have, however, demonstrated that the removal rate of the second and subsequent esterase labile protecting groups significantly slows down after the first protecting group is removed due to the negative charge on the phosphodiester intermediate, which disturbs the catalytic site of the enzyme. In this thesis, esterase labile protecting group strategies where the issue of retardation could be avoided were studied. Prodrug candidates of antiviral nucleotides were synthesized and kinetic studies on the chemical and enzymatic stability were carried out. In the synthesized compounds, the second protecting group is cleaved from the monophosphate some other mechanism than esterase triggered activation or the structure of prodrug requires only one protecting group. In addition, esterase labile protecting group which is additionally thermally removable was studied. This protecting group was cleaved from oligomeric phosphodiesters both enzymatically and thermally and seems most attractive of the studied phosphate protecting groups. However, the rate of the thermal removal still is too slow to allow efficient protection of longer oligonucleotides and needs optimization. Key words: antiviral, nucleotide, prodrug, protecting group, biodegradable

How Lean Six Sigma and Agile principles optimize ITIL-based processes

Imagine the potential implications of an organization whose business and IT processes are well aligned and are capable of reactively and proactively responding to the external and internal changes. The Philips IT Infrastructure and Operations department (I&O) is undergoing a series of transformation activities to help Philips business keeping up with the changes. I&O would serve a critical function in any business sectors; given that the I&O’s strategy switched from “design, build and run” to “specify, acquire and performance manage”, that function is amplified. In 2013, I&O’s biggest transforming programme I&O Futures engaged multiple interdisciplinary departments and programs on decommissioning legacy processes and restructuring new processes with respect to the Information Technology Internet Library (ITIL), helping I&O to achieve a common infrastructure and operating platform (CI&OP). The author joined I&O Futures in the early 2014 and contributed to the CI&OP release 1, during which a designed model Bing Box and its evaluations were conducted through the lens of six sigma’s structured define-measure-analyze-improve-control (DMAIC) improvement approach. This Bing Box model was intended to firstly combine business and IT principles, namely Lean IT, Agile, ITIL best practices, and Aspect-oriented programming (AOP) into a framework. Secondly, the author implemented the modularized optimization cycles according to the defined framework into Philips’ ITIL-based processes and, subsequently, to enhance business process performance as well as to increase efficiency of the optimization cycles. The unique of this thesis is that the Bing Box model not only provided comprehensive optimization approaches and principles for business process performance, but also integrated and standardized optimization modules for the optimization process itself. The research followed a design research guideline that seek to extend the boundaries of human and organizational capabilities by creating new and innovative artifacts. The Chapter 2 firstly reviewed the current research on Lean Six Sigma, Agile, AOP and ITIL, aiming at identifying the broad conceptual bases for this study. In Chapter 3, we included the process of constructing the Bing Box model. The Chapter 4 described the adoption of Bing Box model: two-implementation case validated by stakeholders through observations and interviews. Chapter 5 contained the concluding remarks, the limitation of this research work and the future research areas. Chapter 6 provided the references used in this thesis.

Macrocospic and physiochemical characterization of a sugarless and gluten-free cake enriched with fibers made from pumpkin seed (Cucurbita maxima, L.) flour and cornstarch

The Consumers' interest for products with caloric reduction has increased, and their development is a technological challenge. The consumption of cakes has grown in importance and the demand for dietary products has stimulated the use of sweeteners and the optimization of bakery products. The consumption of fibers is related to chronic diseases prevention. Pumpkin seeds (maximum Cucurbita, L.), rich in fibers, can be used as a source of fiber in food products. A gluten-free diet is not easy to follow since gluten free products are not always available. The objective of this work was to perform a physicochemical characterization of cakes prepared with flours blends (FB) based on Pumpkin Seed Flour (PSF). The cakes were elaborated with FB in the ratios of 30:70 (C30) and 40:60 (C40) of PSF and cornstarch (CS), respectively. The results showed gluten absence and near-neutral pH. The chemical analysis of C30 and B40 showed increase of ashes, lipids, proteins, and insoluble dietary fiber and a decrease in the content of carbohydrates and calories. The chemical composition of C40 presented the greatest content of lipids, proteins, and dietary fibers, the lowest content of calories, and the best physical parameters. Therefore, both products proved suitable for human consumption.

Energy Efficiency in Electrical Drive Systems: Technical potentials, barriers and policy approaches for small and medium industries in Ghana

Today industries and commerce in Ghana are facing enormous energy challenge. The pressure is on for industries to reduce energy consumption, lower carbon emissions and provide se-cured power supply. Industrial electric motor energy efficiency improvement is one of the most important tools to reduce global warming threat and reduce electricity bills. In order to develop a strategic industrial energy efficiency policy, it is therefore necessary to study the barriers that inhibit the implementation of cost – effective energy efficiency measures and the driving forces that promote the implementation. The aim of this thesis is to analyse the energy consumption pattern of electric motors, study factors that promote or inhibit energy efficiency improvements in EMDS and provide cost – effective solutions that improve energy efficiency to bridge the existing energy efficiency gap in the surveyed industries. The results from this thesis has revealed that, the existence of low energy efficiency in motor-driven systems in the surveyed industries were due to poor maintenance practices, absence of standards, power quality issues, lack of access to capital and limited awareness to the im-portance of energy efficiency improvements in EMDS. However, based on the results pre-sented in this thesis, a policy approach towards industrial SMEs should primarily include dis-counted or free energy audit in providing the industries with the necessary information on potential energy efficiency measures, practice best motor management programmes and estab-lish a minimum energy performance standard (MEPS) for motors imported into the country. The thesis has also shown that education and capacity development programmes, financial incentives and system optimization are effective means to promote energy efficiency in elec-tric motor – driven systems in industrial SMEs in Ghana

Optimization of trial wave functions for use in quantum Monte Carlo with application to LiH

Methods for both partial and full optimization of wavefunction parameters are explored, and these are applied to the LiH molecule. A partial optimization can be easily performed with little difficulty. But to perform a full optimization we must avoid a wrong minimum, and deal with linear-dependency, time step-dependency and ensemble-dependency problems. Five basis sets are examined. The optimized wavefunction with a 3-function set gives a variational energy of -7.998 + 0.005 a.u., which is comparable to that (-7.990 + 0.003) 1 of Reynold's unoptimized \fin ( a double-~ set of eight functions). The optimized wavefunction with a double~ plus 3dz2 set gives ari energy of -8.052 + 0.003 a.u., which is comparable with the fixed-node energy (-8.059 + 0.004)1 of the \fin. The optimized double-~ function itself gives an energy of -8.049 + 0.002 a.u. Each number above was obtained on a Bourrghs 7900 mainframe computer with 14 -15 hrs CPU time.

Synthesis of new zirconium diketiminate complexes and catalytic applications

Résumé: Dans le but de préparer des complexes de Zr pour la catalyse homogène de la polymérisation des lactides et de l’hydroamination des olefines, l’elaboration et l’optimisation d’une méthode systématique et efficace de synthèse des ligands dikétimines ayant différents substituants alkyles (R) à la position N,N’ a été realisée. Des dikétimines (nacnacRH) symétriques ont été obtenus avec une pureté de plus de 95 % et un rendement de 65 % lorsque R = Me et des rendements allant de 80 à 95 % lorsque le groupe R = n-Pr, i-Pr, i-Bu, Bu, Cy et (+)-CH(Me)Ph. La synthèse des dikétimines ayant des substituants N-alkyls différents, dite asymétriques, donne toujours un mélange statistique de trois ligands: nacnacR,R’H, nacnacR,RH et nacnacR’,R’H qui n’ont pu être separés. Seuls les dikétimines asymétriques avec un substituant N-alkyl et un autre N-aryl (nacnacR,ArH) ont été obtenus avec des rendements plus élevés que celui du mélange statistique. Par la suite, la complexation de ces ligands bidentés au Zr, la caractérisation de ces complexes et l’investigation de la réactivité ont été étudiés. Les complexes de Zr de type (nacnacR)2ZrCl2 ont été obtenus par deux voies de synthèse principales: la première consiste à traiter le sel de lithium du ligand avec le ZrCl4. La seconde est la réaction du ligand avec les complexes neutres d’alkyl-zirconium(IV) par protonation de l'alkyle coordonné. En solution, les complexes obtenus de (nacnacR)2ZrX2 possèdent un comportement dynamique via un « Bailar-twist » et les paramètres d'activation de cette isomérisation ont été calculés. Le complexe octaèdrique (nacnacBn)2ZrCl2 n'est pas réactif dans la carbozirconation et son alkylation n'était pas possible par l’échange des chlorures avec les alkyles. L’analogue diméthylé (nacnacBn)2ZrMe2 peut être préparé par alkylation du ZrCl4 avant la complexation du ligand. On a également observé que ce dernier n’est pas réactif dans la carbozirconation. L‘analogue diéthoxyde (nacnacBn)2Zr(OEt)2 est obtenu par échange des diméthyles avec les éthoxydes. La polymérisation du lactide avec celui-ci en tant que précurseur est relativement lente et ne peut être effectuée que dans le monomère fondu. Par conséquent, pour résoudre les problèmes rencontrés avec les complexes de zirconium (dikétiminates non-pontés), un ligand dikétimines pontés par le diaminocyclohexane, (±)-C6H10(nacnacXylH)2, LH2, (Xyl = 2,6-diméthylphényle) a été préparé. La complexation de ce ligand tetradenté au metal a été réalisée par deux voies de synthèse; la première est la réaction du sel de lithium de ce ligand avec le ZrCl4(THF)2. La deuxième est la déprotonation du ligand neutre avec le Zr(NMe2)4 et l’élimination du diméthylamine. Des complexes du type: (±)-C6H10(nacnacXylH)2ZrX2 avec X = Cl, NMe2 ont été obtenus. Les ligands de chlorure sont dans ce cas facilement remplaçables par des éthoxydes ou des méthyles. On a observé l’activité la plus élevée jamais observée pour un complexe d’un métal du groupe 4 avec le complexe de (±)-C6H10(nacnacXylH)2Zr(OEt)2 dans la polymérisation de lactide. L'étude cinétique a montré que la loi de vitesse est du premier ordre en catalyseur et en monomère et la constante de vitesse est k = 14 (1) L mol-1 s-1. L'analyse des polymères a montré l’obtention de masses moléculaires faibles et l’abscence de stéréocontrôle. La réaction de (±)-C6H10(nacnacXylH)2ZrCl2 avec le triflate d’argent donne le (±)-C6H10(nacnacXylH)2Zr(OTf)2. Le complexe bis-triflate obtenu possède une activité catalytique elevée pour les additions du type aza-Michael. L’utilisation du R,R-C6H10(nacnacXylH)2Zr(OTf)2 énantiopur comme catalyseur, dans les additions du type aza-Michael asymétriques donne le produit desiré avec un excès énantiomérique de 19%.

Collaborative design procedures for architects and engineers

This book argues for novel strategies to integrate engineering design procedures and structural analysis data into architectural design. Algorithmic procedures that recently migrated into the architectural practice are utilized to improve the interface of both disciplines. Architectural design is predominately conducted as a negotiation process of various factors but often lacks rigor and data structures to link it to quantitative procedures. Numerical structural design on the other hand could act as a role model for handling data and robust optimization but it often lacks the complexity of architectural design. The goal of this research is to bring together robust methods from structural design and complex dependency networks from architectural design processes. The book presents three case studies of tools and methods that are developed to exemplify, analyze and evaluate a collaborative work flow.

From dichotic listening to the irrelevant sound effect: a behavioural and neuroimaging analysis of the processing of unattended speech

The assumption that ignoring irrelevant sound in a serial recall situation is identical to ignoring a non-target channel in dichotic listening is challenged. Dichotic listening is open to moderating effects of working memory capacity (Conway et al., 2001) whereas irrelevant sound effects (ISE) are not (Beaman, 2004). A right ear processing bias is apparent in dichotic listening, whereas the bias is to the left ear in the ISE (Hadlington et al., 2004). Positron emission tomography (PET) imaging data (Scott et al., 2004, submitted) show bilateral activation of the superior temporal gyrus (STG) in the presence of intelligible, but ignored, background speech and right hemisphere activation of the STG in the presence of unintelligible background speech. It is suggested that the right STG may be involved in the ISE and a particularly strong left ear effect might occur because of the contralateral connections in audition. It is further suggested that left STG activity is associated with dichotic listening effects and may be influenced by working memory span capacity. The relationship of this functional and neuroanatomical model to known neural correlates of working memory is considered.

Parallel performance and scalability experiments with the Danish Eulerian Model on the EPCC supercomputers

The Danish Eulerian Model (DEM) is a powerful air pollution model, designed to calculate the concentrations of various dangerous species over a large geographical region (e.g. Europe). It takes into account the main physical and chemical processes between these species, the actual meteorological conditions, emissions, etc.. This is a huge computational task and requires significant resources of storage and CPU time. Parallel computing is essential for the efficient practical use of the model. Some efficient parallel versions of the model were created over the past several years. A suitable parallel version of DEM by using the Message Passing Interface library (AIPI) was implemented on two powerful supercomputers of the EPCC - Edinburgh, available via the HPC-Europa programme for transnational access to research infrastructures in EC: a Sun Fire E15K and an IBM HPCx cluster. Although the implementation is in principal, the same for both supercomputers, few modifications had to be done for successful porting of the code on the IBM HPCx cluster. Performance analysis and parallel optimization was done next. Results from bench marking experiments will be presented in this paper. Another set of experiments was carried out in order to investigate the sensitivity of the model to variation of some chemical rate constants in the chemical submodel. Certain modifications of the code were necessary to be done in accordance with this task. The obtained results will be used for further sensitivity analysis Studies by using Monte Carlo simulation.

Influence of culture conditions on mycelial growth and bioluminescence of Gerronema viridilucens

Herein we describe a procedure for measuring the total light emission of the naturally bioluminescent tropical fungus Gerronema viridilucens and the optimization of culture conditions using multivariate factorial ANOVA. Cultures growing on an agar surface in 35 mm Petri dishes at 90% humidity show optimal bioluminescence emission at 25 degrees C in the presence of 1.0% sugar cane molasses, 0.10% yeast extract and pH 6.0 (nonbuffered). Temperature and pH are the most important factors for both mycelial growth and bioluminescence.

Developing a Communication link between Agents and cross Platform IDE

The main objective of this thesis work is to develop communication link between Runrev Revolution (IDE) and JADE (Multi-Agent System) through Socket programming using TCP/IP layer. These two independent platforms are connected using socket programming technique. Socket programming is considered to be newly emerging technology among these two platforms, the work done in this thesis work is considered to be a prototype.A Graphical simulation model is developed by salixphere (Company in Hedemora) to simulate logistic problems using Runrev Revolution (IDE). The simulation software/program is called “BIOSIM”. The logistic problems are complex, and conventional optimization techniques are unlikely very successful. “BIOSIM” can demonstrate the graphical representation of logistic problems depending upon the problem domains. As this simulation model is developed in revolution programming language (Transcript) which is dynamically typed and English-like language, it is quite slow compared to other high level programming languages. The object of this thesis work is to add intelligent behaviour in graphical objects and develop communication link between Runrev revolution (IDE) and JADE (Multi-Agent System) using TCP/IP layers.The test shows the intelligent behaviour in the graphical objects and successful communication between Runrev Revolution (IDE) and JADE (Multi-Agent System).

Photovoltaic System Design for a Contaminated Area in Falun – Comparison of South and East- West Layout

In this thesis the solar part of a large grid-connected photovoltaic system design has been done. The main purpose was to size and optimize the system and to present figures helping to evaluate the prospective project rationality, which can potentially be constructed on a contaminated area in Falun. The methodology consisted in PV market study and component selection, site analysis and defining suitable area for solar installation; and system configuration optimization based on PVsyst simulations and Levelized Cost of Energy calculations. The procedure was mainly divided on two parts, preliminary and detailed sizing. In the first part the objective was complex, which included the investigation of the most profitable component combination and system optimization due to tilt and row distance. It was done by simulating systems with different components and orientations, which were sized for the same 100kW inverter in order to make a fair comparison. For each simulated result a simplified LCOE calculation procedure was applied. The main results of this part show that with the price of 0.43 €/Wp thin-film modules were the most cost effective solution for the case with a great advantage over crystalline type in terms of financial attractiveness. From the results of the preliminary study it was possible to select the optimal system configuration, which was used in the detailed sizing as a starting point. In this part the PVsyst simulations were run, which included full scale system design considering near shadings created by factory buildings. Additionally, more complex procedure of LCOE calculation has been used here considered insurances, maintenance, time value of money and possible cost reduction due to the system size. Two system options were proposed in final results; both cover the same area of 66000 m2. The first one represents an ordinary South faced design with 1.1 MW nominal power, which was optimized for the highest performance. According to PVsyst simulations, this system should produce 1108 MWh/year with the initial investment of 835,000 € and 0.056 €/kWh LCOE. The second option has an alternative East-West orientation, which allows to cover 80% of occupied ground and consequently have 6.6 MW PV nominal power. The system produces 5388 MWh/year costs about 4500,000 € and delivers electricity with the same price of 0.056 €/kWh. Even though the EW solution has 20% lower specific energy production, it benefits mainly from lower relative costs for inverters, mounting and annual maintenance expenses. After analyzing the performance results, among the two alternatives none of the systems showed a clear superiority so there was no optimal system proposed. Both, South and East-West solutions have own advantages and disadvantages in terms of energy production profile, configuration, installation and maintenance. Furthermore, the uncertainty due to cost figures assumptions restricted the results veracity.

Optimization Of Groundwater Remediation With New Efficient Parallel Algorithm For Global Optimization

Application of optimization algorithm to PDE modeling groundwater remediation can greatly reduce remediation cost. However, groundwater remediation analysis requires a computational expensive simulation, therefore, effective parallel optimization could potentially greatly reduce computational expense. The optimization algorithm used in this research is Parallel Stochastic radial basis function. This is designed for global optimization of computationally expensive functions with multiple local optima and it does not require derivatives. In each iteration of the algorithm, an RBF is updated based on all the evaluated points in order to approximate expensive function. Then the new RBF surface is used to generate the next set of points, which will be distributed to multiple processors for evaluation. The criteria of selection of next function evaluation points are estimated function value and distance from all the points known. Algorithms created for serial computing are not necessarily efficient in parallel so Parallel Stochastic RBF is different algorithm from its serial ancestor. The application for two Groundwater Superfund Remediation sites, Umatilla Chemical Depot, and Former Blaine Naval Ammunition Depot. In the study, the formulation adopted treats pumping rates as decision variables in order to remove plume of contaminated groundwater. Groundwater flow and contamination transport is simulated with MODFLOW-MT3DMS. For both problems, computation takes a large amount of CPU time, especially for Blaine problem, which requires nearly fifty minutes for a simulation for a single set of decision variables. Thus, efficient algorithm and powerful computing resource are essential in both cases. The results are discussed in terms of parallel computing metrics i.e. speedup and efficiency. We find that with use of up to 24 parallel processors, the results of the parallel Stochastic RBF algorithm are excellent with speed up efficiencies close to or exceeding 100%.

Automatic layout generation of static CMOS circuits targeting delay and power

The evolution of integrated circuits technologies demands the development of new CAD tools. The traditional development of digital circuits at physical level is based in library of cells. These libraries of cells offer certain predictability of the electrical behavior of the design due to the previous characterization of the cells. Besides, different versions of each cell are required in such a way that delay and power consumption characteristics are taken into account, increasing the number of cells in a library. The automatic full custom layout generation is an alternative each time more important to cell based generation approaches. This strategy implements transistors and connections according patterns defined by algorithms. So, it is possible to implement any logic function avoiding the limitations of the library of cells. Tools of analysis and estimate must offer the predictability in automatic full custom layouts. These tools must be able to work with layout estimates and to generate information related to delay, power consumption and area occupation. This work includes the research of new methods of physical synthesis and the implementation of an automatic layout generation in which the cells are generated at the moment of the layout synthesis. The research investigates different strategies of elements disposition (transistors, contacts and connections) in a layout and their effects in the area occupation and circuit delay. The presented layout strategy applies delay optimization by the integration with a gate sizing technique. This is performed in such a way the folding method allows individual discrete sizing to transistors. The main characteristics of the proposed strategy are: power supply lines between rows, over the layout routing (channel routing is not used), circuit routing performed before layout generation and layout generation targeting delay reduction by the application of the sizing technique. The possibility to implement any logic function, without restrictions imposed by a library of cells, allows the circuit synthesis with optimization in the number of the transistors. This reduction in the number of transistors decreases the delay and power consumption, mainly the static power consumption in submicrometer circuits. Comparisons between the proposed strategy and other well-known methods are presented in such a way the proposed method is validated.