The importance of porous materials has risen substantially in the last few decades due to their ability to reduce the size and cost of bioanalytical devices and fuel cells. First, this work aims to describe the fabrication of nanoporous gold (NPG) electrodes that are resistant to electrode passivation due to fibrinogen biofouling in redox solutions. The effect on potentiometric and voltammetric experiments was seen as a deviation from ideal behavior on planar gold electrodes, whereas NPG electrodes were consistently behaving in a Nernstian fashion at low concentrations of ferri-ferrocyanide (£100 mM). An improvement in electrode behavior on NPG electrodes versus planar gold was seen in solutions containing ascorbic acid as well as blood plasma. Second, cost effective NPG electrodes were fabricated using a glass substrate to test the response in the presence of a variety of redox molecules. The optical transparency of these electrodes allowed for microdroplet measurements to be made using an inverted microscope in several redox solutions for validation and subsequent biological applicability. Nernstian behavior was demonstrated for all one- and two-electron transfer systems in both poised and unpoised solutions. All experiments were conducted using volumes between 280 and 1400 pL producing rapid results in less than one minute. Third, in order to decrease the requirement for complex instrumentation, microdroplet fabrication technique was used to create mini-nanoporous gold (mNPG) electrodes on glass capillary tubes. The cylindrical shape of the electrodes allowed for testing in sample volumes of 100 mL. The response to ferri-ferrocyanide, ascorbic acid, cysteine, and uric acid was then investigated with Nernstian behavior shown. However, the mNPG electrodes were insensitive to glucose and hydrogen peroxide. In order to increase the sensitivity of the electrodes, a minimal amount of platinum was electrodeposited onto the NPG surface using a low concentration of platinum salt (0.75 mM) for a short deposition time (2 seconds) producing a Nernstian response to both glucose and hydrogen peroxide. Lastly, to test the viability of crossover applications, the platinum incorporated NPG electrode was employed as a fuel cell anode material, testing their oxidation capability with methanol, ethanol, and formic acid.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2006. / Includes abstract in English. Includes bibliographical references.

The aim of this thesis is the development of solid contact ion selective electrodes, ISEs, where the transducer layer is made of a network of carbon nanotubes.Potentiometric classical ion selective electrodes (ISEs) have been used for analytical applications since the beginning of 1900's. Determination of pH by a glass membrane ion selective electrode emerged at the beginning, being the first ISEs developed. pH glass electrode is still one the most useful and robust sensors for routine measurements both in laboratories and industries.Throughout the years, new technologies, ideas and designs have been developed and incorporated successfully in the potentiometric fields so as to provide answers to the new society's needs. Therefore, the ion selective electrodes developed in this thesis are a step further in the progress of ISEs and must be considered as products of the scientific envisioning, growth, and interdisciplinary cooperation of many research teams over many years of continuous efforts. The sensing part can be regarded nowadays as well developed, although it has been during only the last few years when considerable improvements have taken place in the development of new polymeric membranes, ionophores and lipophilic ions. Moreover, the understanding of the theoretical sensing mechanism has been a powerful solid backbone in the rise of ISEs. Miniaturization of classical ISEs requires making all solid contact electrodes to avoid the intrinsic drawbacks of the inner solution. In this manner, the transduction layer has been the focus of attention for the two last decades. New solid contact transducers having the capacity to convert an ionic current into an electronic current have been emerging. Within them, conducting polymers have played an important role in the transduction of the potentiometric signal, being the most used in solid contact ion selective electrodes (SC-ISEs) up to now. However, the behaviour of conducting polymers can be further improved. For instance, their sensitivity to light one of main operational issues yet to be solved.In the present context of searching for new materials able to transduce potentiometric signals we selected and tested carbon nanotubes (CNTs). CNTs, which were rediscovered by Ijima in 1991, display excellent electronic properties in terms of signal transduction. In addition, due to their chemical reactivity CNTs can be easily functionalized with receptors or other functional groups. In fact, depending on the type of functionalization the macroscopic and microscopic properties of CNTs can be drastically changed. This nanostructured material had not been used previously as a solid contact material in ISEs.The main aim of this thesis is to demonstrate that CNTs can act as a clean and efficient transducer in SC-ISEs overcoming the drawbacks displayed by the previously assayed solid contact materials. The developed electrodes were used in different conditions to determine several ions in different sample types, demonstrating the capabilities of this nanostructured material.The thesis has been structured in different chapters, each one containing the following information:· Chapter 1 provides a short historical overview of potentiometric ISEs. The evolution from the "classical ISEs" to the SC-ISEs is briefly illustrated. Once the motivation for thesis is described, the general and specific objectives of the thesis are reported.· Chapter 2 reports the scientific foundations of the developed electrodes. All components of the ISE, sensing layer, transducers and detection systems are introduced. Analytical performance characteristics of ISEs are also described.· Chapter 3 corresponds to the experimental part. Reagents, protocols, procedures and instruments used in the thesis are reported.· Chapter 4 provides the demonstration that CNTs can act as a transducer layer in SC-ISEs. The first SC-ISEs based on CNTs are characterized by electrochemical and optical techniques.· Chapter 5 contains the experimental results that lead to the elucidation of the possible transduction mechanism of CNTs in SC-ISEs. Electrochemical impedance spectroscopy (EIS) is employed as the main characterization technique. · Chapter 6 is composed of four sections reporting different analytical applications. In the first section, the common pH electrode is developed using a solid contact technology based on CNTs. In the second section, the development of SC-ISEs based on a new synthetic ionophore selective to choline, and CNTs as transducers is shown. In the third section, watertight and pressure-resistant SC-ISEs based on CNTs are developed and tested in aquatic research to obtain information about the gradient profiles along the depth of the lakes. In the fourth section, SC-ISEs based on CNTs are adapted for the on-line control of a denitrification catalytic process.· Chapter 7 reports the possibilities of miniaturization of the SC-ISEs based on CNTs to reach a nanometric electrode. Potentiometric and optical characterizations are described in this section. Moreover, a discussion about the limitations of the real miniaturization in potentiometry is undertaken.· Chapter 8 points out the conclusions of the thesis. In addition, future prospects are suggested.· Finally, several appendices are added to complete the doctoral thesis. / El principal objetivo de esta tesis es el desarrollo de electrodos selectivos de iones de contacto sólido, ESIs-CS, utilizando como capa transductora una red compuesta de nanotubos de carbono.Los electrodos potenciométricos selectivos de iones han sido utilizados en aplicaciones analíticas desde comienzos de 1900. La determinación de pH mediante electrodos de vidrio selectivo de iones fue el primer ESI desarrollado. Hoy en día, el electrodo de vidrio para la determinación de pH es todavía uno de los más útiles y robustos sensores utilizados en mediciones rutinarias tanto en laboratorios como en industrias.A lo largo de los años, nuevas tecnologías, ideas y diseños han sido desarrollados e incorporados satisfactoriamente en el campo potenciométrico proporcionando soluciones a las necesidades en continua evolución de la sociedad. De esta manera, los electrodos selectivos de iones desarrollados en esta tesis son un paso más en el progreso de los ESIs y deben ser considerados como el producto de una sólida base científica, del crecimiento y de la cooperación interdisciplinaria de diversos grupos de investigación durante varios años.La parte del sensor donde tiene lugar el reconocimiento químico y donde se genera el potencial dependiente de la muestra en estudio en los ESIs se puede considerar, en estos días, ampliamente desarrollada, aunque considerables mejoras han tenido lugar durante los últimos años, especialmente en el desarrollo de nuevas membranas poliméricas, ionóforos e iones lipofílicos. Sobretodo, el estudio y la comprensión del mecanismo teórico del sensor ha sido muy importante en el crecimiento y desarrollo de los ESIs.El concepto de electrodos selectivos de iones de estado sólido surge como requisito vital para evitar las intrínsecas desventajas de la solución interna, en el proceso de miniaturización de los ESIs clásicos. De esta forma, la capa transductora ha sido el principal punto de atención durante dos décadas. Así, nuevos transductores de contacto sólido con la capacidad de convertir una corriente iónica en una corriente electrónica han sido desarrollados. Entre ellos, los polímeros conductores han jugado un importante papel en la transducción de la señal potenciométrica, siendo éstos los más empleados en los electrodos selectivos de iones de contacto sólido (ESIs-CS). Sin embargo el comportamiento de los polímeros conductores puede ser mejorado. Por ejemplo, la sensibilidad hacia la luz de estos materiales es un inconveniente todavía no resuelto. En este contexto de investigación de nuevos materiales capaces de actuar como transductor de una señal potenciométrica, se han escogido y estudiado los nanotubos de carbono (NTCs) como transductores. Los NTCs fueros redescubiertos por Ijima en 1991, y muestran excelentes propiedades electrónicas en términos de traducción de señal. Además, debido a su reactividad química, los NTCs pueden ser fácilmente funcionalizados con receptores u otros grupos funcionales. De hecho, sus propiedades macroscópicas y microscópicas pueden ser afectadas drásticamente dependiendo del tipo y grado de funcionalización. Este material nanoestructurado no había sido previamente utilizado como transductor en ISEs.El principal propósito de esta tesis es demostrar que los nanotubos de carbono pueden actuar de forma eficiente como transductor en electrodos selectivos de iones de estado sólido logrando vencer las desventajas de los transductores previamente mencionados. Los electrodos desarrollados fueron usados en diferentes condiciones para determinar distintos iones en diversos tipos de sistemas, demostrando las extraordinarias capacidades de este material nanoestructurado. Esta tesis ha sido estructurada en capítulos que contienen la siguiente información:· El Capítulo 1 proporciona una breve visión histórica de lo electrodos potenciométricos selectivos de iones. Se ilustra la evolución desde los "clásicos ESIs" hasta los actuales "ESIs-CS". Además se señalan en esta sección los objetivos generales y específicos. · El Capitulo 2 contiene las bases científicas de los electrodos desarrollados. Se introducen todos los componentes que integran un ESI, tales como: capa reconocedora, capa transductora y sistema de detección. A continuación se describen los parámetros analíticos de calidad de los ESIs. · El Capitulo 3 describe la parte experimental. Se recogen los reactivos, protocolos, procedimientos e instrumentos usados a lo largo de la tesis.· El Capitulo 4 provee de la demostración de que los NTCs pueden actuar eficientemente como capa transductora en SC-ISEs. Se caracteriza el primer ESI-CS integrado por NTCs mediante técnicas ópticas y electroquímicas.· El Capitulo 5 contiene los resultados experimentales que permiten la posible elucidación del mecanismo de transducción de los NTCs en los ESIs-CS. La Espectroscopia de Impedancia Electroquímica (ESI) es utilizada como la principal técnica de caracterización. · El Capitulo 6 está integrado por cuatro secciones con diferentes aplicaciones analíticas. En la primera sección, se desarrolla un electrodo de pH que usa NTCs como nueva tecnología transductora en ESIs-CS. En la segunda sección se muestra el desarrollo de un ESI-CS integrado por un ionóforo sintético selectivo a colina, y NTCs como transductores. En la tercera sección, ESIs-CS basados en NTCs, resistentes a altas presiones y totalmente herméticos, se desarrollan y prueban en investigaciones acuáticas con la finalidad de obtener información sobre los gradientes de concentración de iones en función de la profundidad de un lago. En la cuarta sección ESIs-CS basados en NTCs se adaptan para el control on-line de un proceso catalítico de desnitrificación.· El Capitulo 7 presenta la posibilidad de la miniaturización de los ESIs-CS basados en NTCs logrando obtener un electrodo nanométrico. Se muestran en esta sección la caracterización óptica y potentiométrica. Además, se discuten las limitaciones de la miniaturización real de los ESIs en potenciometría.· El Capitulo 8 contiene las conclusiones de la tesis. Adicionalmente, se sugieren las perspectivas futuras del trabajo presentado.· Finalmente, se añaden algunos apéndices como complemento de la tesis doctoral.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2005. / Includes abstract in English. Includes bibliographical references. Electronic copy also available.

Charles University Faculty of Pharmacy in Hradec Králové Department of biophysics and physical chemistry Author: Pavla Tomanová Supervisor: Ing. Vladimír Kubíček, CSc. Thesis title: Physico-Chemical properties of drugs This thesis deals with measuring dissociation constants (the pKa value) and the lipophilicity of nitrogenous heterocycle derivatives produced at the Faculty of Pharmacy in Hradec Králové. Two methods were used to determine the pK value: potentiometric titration and spectrophotometry. Potentiometric titration almost invariably produced relatively exact results, however the results of pK value obtained by spectrophotometry were sometimes difficult to replicate. Dissociation constants were compared on the basis of the method applied, and also with the theoretically determined dissociation constant calculated by means of the ChemDraw Ultra 12.0 software. The results obtained by the two experimental methods turned out to be very similar, corresponding to the theoretical pK value. Lipophilicity is another essential property of drugs tested in the preclinical stage. It specifies the aqueous or lipophilic phase affinity of a drug, substantially affecting the drug's ADMET in organism. Lipophilicity was determined on the basis of capacity factor value identified by RP-HPLC measurement using...

Submitted by Geyciane Santos (geyciane_thamires@hotmail.com) on 2015-12-02T20:20:33Z No. of bitstreams: 1 Dissertação - Arlesson Freire de Lima.pdf: 1069637 bytes, checksum: 3aea5b6e8da4bd59f2332f51e3fc7ece (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-12-03T17:56:35Z (GMT) No. of bitstreams: 1 Dissertação - Arlesson Freire de Lima.pdf: 1069637 bytes, checksum: 3aea5b6e8da4bd59f2332f51e3fc7ece (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-12-03T18:14:35Z (GMT) No. of bitstreams: 1 Dissertação - Arlesson Freire de Lima.pdf: 1069637 bytes, checksum: 3aea5b6e8da4bd59f2332f51e3fc7ece (MD5) / Made available in DSpace on 2015-12-03T18:14:35Z (GMT). No. of bitstreams: 1 Dissertação - Arlesson Freire de Lima.pdf: 1069637 bytes, checksum: 3aea5b6e8da4bd59f2332f51e3fc7ece (MD5) Previous issue date: 2015-07-31 / Não informada / In this paper, we propose the determination of lansoprazole content, selective inhibitor of H + / K + -ATPase gastric using titration based on digital image (Digital Image-Based Titration). The DIB system uses a webcam to acquisition of digital images based on the color system RGB (Red-Green-Blue). During the titration procedure the method was applied to the acid-base titration of the drug lansoprazole with hydrochloric acid. The titration was performed by the DIB, and by potentiometry. In DIB methodology for each volume of titrant added an image was captured and manipulated to obtaining the standard values (N=√R̅2+G̅2+B̅2). The spent volume of titrant to reach the equivalence point was obtained from the second derivative of the titration curve. The results of the samples showed no statistically significant differences at the 95% confidence level was observed after applying the paired t test (tcalculado = 0,439 e tcrítico = 2,353). The relative standard deviations using the DIB methodology with the exception of Sample C, was below 1.0%. / Neste trabalho, propõe-se a determinação do teor de lansoprazol, agente inibidor seletivo da H+/K+-ATPase gástrica, utilizando titulação baseada em imagem digital (Digital Image-Based Titration). O sistema DIB utiliza uma webcam para aquisição das imagens digitais com base no sistema de cor RGB (Red-Green-Blue). Durante o procedimento de titulação o método foi aplicado na titulação ácido-base do fármaco lansoprazol com o ácido clorídrico. A titulação foi realizada por DIB e por potenciometria. Na metodologia DIB para cada volume do titulante adicionado uma imagem era capturada e manipulada para obtenção dos valores da norma (N=√R̅2+G̅2+B̅2). O volume gasto de titulante para atingir o ponto de equivalência, foi obtido a partir da segunda derivada da curva de titulação. Os resultados obtidos das amostras não apresentaram nenhuma diferença estatística significativa no nível de confiança de 95 % que foi verificada após aplicar o teste t emparelhado (tcalculado = 0,439 e tcrítico = 2,353). Os desvios padrão relativos utilizando a metodologia DIB, com exceção da amostra C, ficaram abaixo de 1,0 %.

Two phosphinic acids were prepared: 1-hydroxy-ethan-1,1-bis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L1 and methylenebis[N,N- bis(karboxymethyl)aminomethyl]phosphinic acid; H6L2 . Acid-base and complexation properties were studied by potenciometric titrations. Complexes of both ligands with Cu2+ ions were studied in detail using UV/VIS spectrometry. Keywords: Organophosphorus synthesis, bisphosphinic acids, coordination properties

In an effort to increase the thermodynamic stability and the kinetic inertness of the complexes, the five new azamacrobicyclic ligands derived from TACN, cyclen, and cyclam have been prepared. The ligands were decorated with phosphinate or phosphonate pendant arms to maintain fast complexation. Since the ascending importance of targeted diagnostic and therapy, the bone-targeted non-bridged cyclam derivative with phosphinate-bis(phosphonate) pendant arm (H5TE1PBP) has also been synthesized. The ligands were studied with respect to their application. The bridged TACN (H2bpbtacn) and cyclen (H4bpbcen) ligands show high macrocyclic basicity (logK1 = 12.25 and 12.70, respectively). The thermodynamic stability of H2bpbtacn with Cu(II) ion is more than ten orders of magnitude lower than that of the NOTA ligand. The stability constants of H4bpbcen with Cu(II) and Zn(II) ions are comparable to those given for the DOTA. The stability of Ln(III)-bpbcen complexes is 7-10 orders of magnitude lower compared to DOTA complexes. For both ligands, the lower thermodynamic stability of the complexes is attributed to the high rigidity of the ligand structure. The bridged cyclam derivatives with phosphonate (H4TE2P), bis(phosphinate) (H4TE2bpin), or phosphinate (H2TE2PH) pendants are characterized by high stability of...

Phosphorus is needed by living organism including humans and plants, to survive. Imbalance in phosphate concentration in human body can result in numerous diseases or disorders while excess phosphorus levels in water bodies like lakes, and rivers, are responsible for the rise in incidence of algal bloom across world. Current commercial phosphate monitoring systems are dominated by colorimetric measurements while electrochemical sensors including potentiometric, amperometric and voltammetric sensors are still in the research phase. Electrochemical sensors require stable reference electrodes for reliable measurements that pose challenges for miniaturization. Solid state potentiometric sensors are widely explored due to their rapid response, easy fabrication and simple electronic measurement system. However, the sensor miniaturization is dependent both on the working and reference electrode. Metal electrodes like cobalt offers advantages such as reagent-free detection, easy to miniaturize but the sensitivity of zero-current potentiometric sensors is limited by the theoretical Nernstian limit and cobalt sensors also require chemical pretreatment in standard solution before measurement. Here, an in situ electrical pretreatment method is proposed to eliminate the need of chemical pretreatment and enhance the sensitivity of cobalt electrodes to -91.4 mV/ decade of phosphate concentration. However, this electrode still needs a reference electrode for reliable measurements. Therefore, this study has demonstrated a chemiresistive sensing platform for solid state detection of phosphate using both enzyme and enzyme-free methods. A rapid prototyping method was developed to pattern the thin metal films (~100 nm thickness) using a bench top plotter cutter. The method was used to fabricate thin gold film contact electrodes for chemiresistors. The thin gold leaf contact electrodes exhibited low-noise and offered a robust, rapid and reproducible manufacturing process for chemiresistors. The chemiresistive sensor showed a wide measuring range (0.5 ppm to 500 ppm) for hydrogen peroxide detection. The sensor was deposited with glucose oxidase to demonstrate the application of the sensor for peroxidase assays to detect glucose in standard buffer solution and human pooled plasma. Phosphate also is detected using pyruvate oxidase in presence of pyruvate to generate hydrogen peroxide as the detectable molecule. Finally, metal phthalocyanines were used to perform enzyme-free phosphate measurements. This work demonstrated the sensor technologies which could be used for in-field phosphate monitoring to prevent algal bloom and it also provides phosphate monitoring methods for rapid detection in medical diagnostics for early diagnosis for diseases like chronic kidney disease and to improve the patient’s outcomes for such diseases. / Thesis / Doctor of Philosophy (PhD) / Phosphorus is an essential element for the survival of living beings including humans and plants because it is needed in multiple physiological pathways and functions like cellular signalling, energy storage, metabolism and maintenance. Therefore, phosphate in the human body is strictly regulated and in disease conditions like chronic kidney disease, and metabolic disorders. It can increase or decrease resulting in ailments and worsening of diseases. Phosphorus is also extensively used in the agricultural field to improve the growth and crop yield. Excess phosphorus from these fertilizers can enter our water sources via agricultural water run-offs leading to the increasing incidences of algal bloom across world. Current phosphorus measuring systems require chemicals which generates toxic waste, needs manual sample collection and transport, and have narrow measuring ranges. There is an urgent need for sensors which would eliminate the need of sample collection and processing, do not require toxic chemicals and could work over a wide detection range. This study presents two solid-state sensor technologies which would simplify the phosphate detection for both environmental and medical diagnostics samples.

Two linear aminodiphosphinates (H3L1 , H5L2 ) and one cyclic aminodiphosphinate (H2L3 ) were prepared and studied. Newly prepared compounds were characterized by NMR, MS and EA (elemental analysis). Acid-base and coordination properties of ligands were studied. Protonation constants and stability constants of complexes with Zn2+ , Ni2+ and Cu2+ metal ions were determined by potentiometry. Keywords Ligands, dissociation constants, potentiometry, phosphinates, complexes.