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.

Paper- and membrane-based ion-modulated electronics

Avhandlingen handlar om pappers- och membranbaserad jonmodulerad elektronik. Målet med forskningen har varit att utveckla billig, miljövänlig och brännbar elektronik, som kan användas i vardagliga engångsprodukter. Baskomponenterna som utvecklas och presenteras i avhandlingen är transistorer och kondensatorer. Mer komplicerad logisk kretselektronik demonstreras också med hjälp av dessa komponenter. Substraten som utnyttjas vid framställningen av dessa elektroniska komponenter är papper och membran. Dessa substrat är flexibla, hållbara, billiga, miljövänliga, etc. och därför väl anpassade för befintliga tryckteknologier. Själva baskomponenterna framställs sedan på dessa substrat genom att trycka flera skikt på varandra, där varje enskilt skikt är ett individuellt material. Detta är möjligt eftersom de organiska materialen som används i dessa komponenter är upplösta i ett lösningsmedel och kan därmed tryckas på samma sätt som ett vanligt bläck. Ett tredimensionellt objekt kan på detta sätt framställas. I avhandlingen presenteras flera olika typer av transistorer, men den gemensamma nämnaren bland dessa är att isolatorn är en jonledare. Denna, ganska ovanliga, transistormodellen har den stora fördelen att lågspänningskomponenter kan relativt enkelt framställas. Det som är speciellt med våra transistorer är att vi har använt miljövänliga jonledare. Detta, bl.a., leder till att våra komponenter visar både god prestanda, tillika som de är miljövänliga. I avhandlingen demonstrerar vi även tryckta superkondensatorer, en motsvarighet till laddningsbara batterier, konstruerade på papper med aktiverat kol och miljövänliga jonledare. De mest komplicerade logiska kretsar som demonstreras i denna avhandling är ring-oscillatorer och 1-bits-minnen konstruerade på papper. --------------------------------------------- Väitöskirja käsittelee paperille ja polymeerikalvolle tulostettua ionimoduloitua elektroniikkaa. Tutkimuksen tavoitteena oli kehittää edullista, ympäristöystävällistä ja polttokelpoista elektroniikkaa, jota voidaan käyttää esim. tavanomaisissa kertakäyttötuotteissa. Väitöskirjassa esitellään erilaisia transistoreita ja kondensaattoreita. Näitä elektronisia peruskomponentteja käyttäen demonstroidaan myös monimutkaisempia loogisia piirejä. Komponenttien valmistuksessa alustana käytettiin paperia ja polymeerikalvoa. Valitut alustat ovat joustavia ja kestäviä, ja ovat siksi hyvin yhteensopivia olemassa olevien tulostusmenetelmien kanssa. Peruskomponentit valmistettiin tulostamalla eri materiaaleja päällekkäin. Komponenteissa käytettävät orgaaniset aineet ovat liuenneessa muodossa musteessa, joka voidaan tulostaa samalla periaatteella kuin mikä tahansa normaali muste. Tällä menetelmällä voidaan valmistaa myös kolmiulotteisia tuotteita. Väitöskirjassa esitellään useita erityyppisiä transistoreita, joissa yhdistävänä tekijänä on ionisesti johtava eriste. Tällaista suhteellisen harvinaista transistorityyppiä käyttämällä voidaan mahdollistaa matala-jännitteisten komponenttien yksinkertainen valmistus. Valmistettujen transistoreiden etu on ionisten nesteiden ympäristöystävällisyys. Elektroniset komponentit ovat täten hyviä suorituskyvyltään, mutteivät haitallisia ympäristölle. Väitöskirjassa demonstroidaan myös tulostettujen superkondensaattoreiden, eli ladattavien paristojen vastineiden, valmistus paperille aktiivihiiltä ja ionisia nesteitä käyttäen. Kaikkein monimutkaisimmat loogiset piirit, jotka tässä väitöskirjassa esitellään, ovat rengasoskillaattorit sekä 1-bittinen paperille valmistettu muisti.

Metal-Ion-Binding Oligonucleotides: High-Affinity Probes for Nucleic Acid Sequences

Small non-coding RNAs have numerous biological functions in cell and are divided into different classes such as: microRNA, snoRNA, snRNA and siRNA. MicroRNA (miRNA) is the most studied non-coding RNA to date and is found in plants, animals and some viruses. miRNA with short sequences is involved in suppressing translation of target genes by binding to their mRNA post-transcriptionally and silencing it. Their function besides silencing of the viral gene, can be oncogenic and therefore the cause of cancer. Hence, their roles are highlighted in human diseases, which increases the interest in using them as biomarkers and drug targets. One of the major problems to overcome is recognition of miRNA. Owing to a stable hairpin structure, chain invasion by conventional Watson-Crick base-pairing is difficult. One way to enhance the hybridization is exploitation of metal-ion mediated base-pairing, i. e. oligonucleotide probes that tightly bind a metal ions and are able to form a coordinative bonds between modified and natural nucleobases. This kind of metallo basepairs containing short modified oligonucleotides can also be useful for recognition of other RNA sequences containing hairpin-like structural motives, such as the TAR sequence of HIV. In addition, metal-ion-binding oligonucleotides will undoubtedly find applications in DNA-based nanotechnology. In this study, the 3,5-dimethylpyrazol-1-yl substituted purine derivatives were successfully incorporated within oligonucleotides, into either a terminal or non-terminal position. Among all of the modified oligonucleotides studied, a 2-(3,5-dimethylpyrazol-1-yl)-6-oxopurine base containing oligonucleotide was observed to bind most efficiently to their unmodified complementary sequences in the presence of both Cu2+ or Zn2+. The oligonucleotide incorporating 2,6-bis(3,5-dimethylpyrazol-1-yl)purine base also markedly increased the stability of duplexes in the presence of Cu2+ without losing the selectivity.

Thermal modelling of commercial lithium-ion batteries

The accelerating adoption of electrical technologies in vehicles over the recent years has led to an increase in the research on electrochemical energy storage systems, which are among the key elements in these technologies. The application of electrochemical energy storage systems for instance in hybrid electrical vehicles (HEVs) or hybrid mobile working machines allows tolerating high power peaks, leading to an opportunity to downsize the internal combustion engine and reduce fuel consumption, and therefore, CO2 and other emissions. Further, the application of electrochemical energy storage systems provides an option of kinetic and potential energy recuperation. Presently, the lithium-ion (Li-ion) battery is considered the most suitable electrochemical energy storage type in HEVs and hybrid mobile working machines. However, the intensive operating cycle produces high heat losses in the Li-ion battery, which increase its operating temperature. The Li-ion battery operation at high temperatures accelerates the ageing of the battery, and in the worst case, may lead to a thermal runaway and fire. Therefore, an appropriate Li-ion battery cooling system should be provided for the temperature control in applications such as HEVs and mobile working machines. In this doctoral dissertation, methods are presented to set up a thermal model of a single Li-ion cell and a more complex battery module, which can be used if full information about the battery chemistry is not available. In addition, a non-destructive method is developed for the cell thermal characterization, which allows to measure the thermal parameters at different states of charge and in different points of cell surface. The proposed models and the cell thermal characterization method have been verified by experimental measurements. The minimization of high thermal non-uniformity, which was detected in the pouch cell during its operation with a high C-rate current, was analysed by applying a simplified pouch cell 3D thermal model. In the analysis, heat pipes were incorporated into the pouch cell cooling system, and an optimization algorithm was generated for the estimation of the optimalplacement of heat pipes in the pouch cell cooling system. An analysis of the application of heat pipes to the pouch cell cooling system shows that heat pipes significantly decrease the temperature non-uniformity on the cell surface, and therefore, heat pipes were recommended for the enhancement of the pouch cell cooling system.

Recognition of nucleic acids by metal ion complexes

Metal-ion-mediated base-pairing of nucleic acids has attracted considerable attention during the past decade, since it offers means to expand the genetic code by artificial base-pairs, to create predesigned molecular architecture by metal-ion-mediated inter- or intra-strand cross-links, or to convert double stranded DNA to a nano-scale wire. Such applications largely depend on the presence of a modified nucleobase in both strands engaged in the duplex formation. Hybridization of metal-ion-binding oligonucleotide analogs with natural nucleic acid sequences has received much less attention in spite of obvious applications. While the natural oligonucleotides hybridize with high selectivity, their affinity for complementary sequences is inadequate for a number of applications. In the case of DNA, for example, more than 10 consecutive Watson-Crick base pairs are required for a stable duplex at room temperature, making targeting of sequences shorter than this challenging. For example, many types of cancer exhibit distinctive profiles of oncogenic miRNA, the diagnostics of which is, however, difficult owing to the presence of only short single stranded loop structures. Metallo-oligonucleotides, with their superior affinity towards their natural complements, would offer a way to overcome the low stability of short duplexes. In this study a number of metal-ion-binding surrogate nucleosides were prepared and their interaction with nucleoside 5´-monophosphates (NMPs) has been investigated by 1H NMR spectroscopy. To find metal ion complexes that could discriminate between natural nucleobases upon double helix formation, glycol nucleic acid (GNA) sequences carrying a PdII ion with vacant coordination sites at a predetermined position were synthesized and their affinity to complementary as well as mismatched counterparts quantified by UV-melting measurements.

Performance Degradation Modelling and Techno-Economic Analysis of Lithium-Ion Battery Energy Storage Systems

Transmission system operators and distribution system operators are experiencing new challenges in terms of reliability, power quality, and cost efficiency. Although the potential of energy storages to face those challenges is recognized, the economic implications are still obscure, which introduce the risk into the business models. This thesis aims to investigate the technical and economic value indicators of lithium-ion battery energy storage systems (BESS) in grid-scale applications. In order to do that, a comprehensive performance lithium-ion BESS model with degradation effects estimation is developed. The model development process implies literature review on lifetime modelling, use, and modification of previous study progress, building the additional system parts and integrating it into a complete tool. The constructed model is capable of describing the dynamic behavior of the BESS voltage, state of charge, temperature and capacity loss. Five control strategies for BESS unit providing primary frequency regulation are implemented, in addition to the model. The questions related to BESS dimensioning and the end of life (EoL) criterion are addressed. Simulations are performed with one-month real frequency data acquired from Fingrid. The lifetime and cost-benefit analysis of the simulation results allow to compare and determine the preferable control strategy. Finally, the study performs the sensitivity analysis of economic profitability with variable size, EoL and system price. The research reports that BESS can be profitable in certain cases and presents the recommendations.

Quest/ion of Identities in African American Feminist Postmodern Drama: A Study of Selected Plays by Suzan-Lori Parks

Innovative and unconventional, Pulitzer Prize-winning playwright Suzan-Lori Parks belongs to the continuum of African American playwrights who have contributed to the quest/ion – the quest for and question – of identities for African Americans. Her plays are sites in which the quest/ion of identities for African Americans is pursued, raised and enacted. She makes use of both page and stage to emphasize the exigency of reshaping African Americans’ identities through questioning the dominant ideologies and metanarratives, delegitimizing some of the prevailing stereotypes imposed on them, drawing out the complicity of the media in perpetuating racism, evoking slavery, lynching and their aftereffects, rehistoricizing African American history, catalyzing reflections on the various intersections of sex, race, class and gender orientations, and proffering alternative perspectives to help readers think more critically about issues facing African Americans. In my dissertation, I approach three plays by Parks – The Death of the Last Black Man in the Whole Entire World (1990), Venus (1996) and Fucking A (2000) – from the standpoints of postmodern drama and African American feminism with a focus on the terrains that reflect the quest/ion of identities for African Americans, especially African American women. I argue that postmodern drama and African American feminism provide the ground for Parks to promote the development of a political agenda in order to call into question a number of dominant ideologies and metanarratives with regard to African Americans and draw upon the roles of those metanarratives as a powerful apparatus of racial and sexual oppressions. I also explore how Parks engages with postmodern drama and African American feminism to incorporate her own mininarratives in the dominant discourses. I argue that Parks in these plays uses postmodern drama and African American feminism to encourage reflections on intersectionality in order to reveal the concerns of African Americans, particularly African American women. Her plays challenge the dominant order of hierarchy and patriarchy, while in some cases urging unity and solidarity between African American men and women by showing how unity and solidarity can help them confront race, class and gender oppressions. Furthermore, I discuss how the utilization of postmodern techniques and devices helps Parks to transform the conventional features of playwriting, to create incredulity toward the dominant systems of oppression and to incorporate her mininarratives within the context of dominant discourses.