>Magister Scientiae - MSc / A study on carbon paste electrode (CPE) materials containing 1-methyl-3-octylimidazolium bis (trifluoromethylsulfonyl) imide [MOIM[Tƒ2N] – a hydrophobic room temperature ionic liquid (IL) - is reported. CPEs with (a) the IL as the only binder (ILCPE) and (b) 1:1 (v/v) IL: paraffin mixture as the binder (ILPCPE) were prepared, characterized, and applied to the electrodeposition of films of multivalent transition metal oxides (MV-TMO) from five precursor ions (Fe2+, Mn2+, Cu2+, Co2+, Ce4+) in aq. KCl. Cyclic voltammetry (CV) showed a potential window of +1.5 V to -1.8 V regardless of the electrode type, including the traditional paraffin CP electrode (PCPE). However, the IL increased the background current by 100-folds relative to paraffin. The electrochemical impedance spectroscopy (EIS) of ILPCPE in aq. KCl (0.1M) revealed two phase angle maxima in contrast with the single maxima for PCPE and ILCP. The study also included the CV and EIS investigation of the electrode kinetics of the Fe(CN)6 3-/4 redox system at these electrodes. The electrodeposition of Fe2+, Co2+, and Mn2+ possibly in the form of the MV-TMOs FexOy, CoxOy, and MnxOy, respectively, onto the electrodes was confirmed by the observation of new and stable cathodic and anodic peaks in a fresh precursor ion –free medium. CVs of H2O2 as a redox probe supported the same conclusions. Both ATR-FTIR spectra and SEM image of surface samples confirmed the formation of electrodeposited films. This study demonstrated that the use of this hydrophobic IL alone or in combination with paraffin as a binder gives viable alternative CPE materials with better performance for the electrodeposition of MV-TMOs films than the paraffin CPE. Thus, in combination with the easy preparation methods and physical “morpheability” in to any shape, these CPEs are potentially more useful in electrochemical technologies based on high surface-area MV-TMO films in general, and MnxOy films in particular.

The proposed Thesis deals with the electrochemical behavior of sulfamethizole on carbon paste electrodes. Sulfamethizole is a sulfonamide antibiotic effective against a number of gram-positive and gram-negative bacteria. In human medicine, the most frequent application is for the treatment of urinary tract. In veterinary medicine, it is used for the and preventive treatment of both aquatic and terrestic animals. Due to the wide utilization and low metabolization, it also presents an environmental burden. The development of quick and sensitive methods for the determination in both biological and pharmaceutical matrices is therefore important. This Thesis deals with the search of optimum conditions for differential pulse voltammetric determination of sulfamethizole in tablets Micturol sedante, used for the treatment of urinary tract. The method uses Britton-Robinson (B-R) buffer pH 7 and reaches detection limit 0,39 µmol·l-1 . Results of the method complied with the manufacturer's information and with the results of spectrophotometric determination. In the other part of the work, conditions for the determination of sulfamethizole determination in urine samples. Fonund conditions were: Lichrospher® RP-18, 100 (5 µm), 125×4 mm, (LichroCART) column, mobile phase B-R buffer pH 3 : methanol (7:3, v/v) and...

7 ABSTRACT (EN) This dissertation thesis is focused on the study of electrochemical properties of new types of carbon paste electrodes (CPE) and carbon fiber rod electrodes (CFRE), which were used for the development of new highly sensitive and selective voltammetric and amperometric methods for the determination of 5-amino-6-nitroquinoline and trans- and cis- isomers of resveratrol. The carbon paste electrodes were compared in terms of size of the microparticles of glassy carbon contained in the paste (diameters 0.4 - 12 µm; 10 - 20 µm; 20 - 50 µm) in comparison with carbon paste electrode consisting of crystalline graphite and solid glassy carbon electrode. The electrochemical properties were tested using potassium hexacyanoferrate in an aqueous supporting electrolyte and 5-amino-6-nitroquinoline (5A6NQ) in a mixed methanol-water supporting electrolyte. The carbon paste electrode was further used in an amperometric detector of a wall-jet type connected in series with a spectrophotometric detector for the development of a new HPLC method with electrochemical detection and spectrophotometric detection for the determination of trans-resveratrol and cis-resveratrol in samples of grains, hulls and leaves of common and tartary buckwheat. The method was optimized and used for the determination of resveratrol in...

Made available in DSpace on 2017-07-24T19:37:58Z (GMT). No. of bitstreams: 1 Introducao.pdf: 4076807 bytes, checksum: 48a9024758e4ef8be57c1dc1d440a82c (MD5) Previous issue date: 2008-03-13 / In this work was developed a methodology for incorporation of platinum particles to carbon black matrices called Eeonomers (Kp0; Kp20 and Kpy20). The characterization of modified materials Kp0/Pt; Kp20/Pt and Kpy20/Pt was performed by SEM / EDX; XRD; TEM and Cyclic Voltammetry (VC). Measures of the SEM coupled to EDX showed that the platinum particles were homogeneous distributed in the carbon matrix. Meanwhile, the average size of nanoparticles were estimated between 3 and 7 nm through calculations with the application of the Scherrer’s equation and were confirmed by MET measurements. The VC confirmed the incorporation of particles by the increase of faradaics current in negative and positive extremes of the potencial scan range assigned to the generation of oxygen and hydrogen due to the presence of platinum incorporated to the modified materials. These modified materials were used in the production of electrodes and were applied in electroanalysis used for determination of dopamine and for oxidation of methanol. The electrodes modified with platinum (EPC/Kp0/Pt, EPC/Kp20/Pt e EPC/Kpy20/Pt) showed no effects of electrooxidation for dopamine, as was expected and therefore, did not justify a modification of the material due to the high cost of platinum. Nevertheless, the electrodes of Kp0/Pt and Kp20/Pt were efficient in electrooxidation of methanol in all concentrations and can be used to replace the smooth platinum, since it increased the number of available active sites even in smaller concentrations investigated. This surface area of available platinum in the modified electrodes was calculated by the difference of integrals of the first and second cycles during the process of cyclical scanning in measures of CO adsorbed considering a load of platinum smooth at 484 μ C.cm2. Key words: Carbon black, Eeonomers, carbon paste electrodes, Cyclic Voltammetry / Neste trabalho desenvolveu-se uma metodologia para incorporação de partículas de platina a matrizes de negro de fumo denominadas de Eeonômeros (Kp0; Kp20 e Kpy20). A caracterização dos materiais modificados Kp0/Pt; Kp20/Pt e Kpy20/Pt foi realizada por MEV/EDX; DRX; MET e Voltametria Cíclica (VC). As medidas de MEV acopladas a EDX mostraram que as partículas de platina estavam distribuídas de forma homogênea na matriz orgânica. Já os tamanhos médios das nanopartículas foram estimados entre 3 e 7 nm através de cálculos com a aplicação da equação de Scherrer e confirmados pelas medidas de MET. A VC confirmou a incorporação das partículas pelo aumento das correntes faradaicas nos extremos negativos e positivos devido à geração de oxigênio e hidrogênio atribuídos à presença da platina incorporada aos materiais modificados. Estes materiais modificados foram utilizados na produção de eletrodos e aplicados em eletroanálise através da técnica de VC e utilizados para determinação da dopamina e oxidação do metanol. Os eletrodos modificados com platina (EPC/Kp0/Pt, EPC/Kp20/Pt e EPC/Kpy20/Pt) não apresentaram efeitos de eletrooxidação para a dopamina como era esperado e, portanto não justificaram a modificação do material devido ao alto custo da platina. Entretanto, os eletrodos de EPC/Kp0/Pt e EPC/Kp20/Pt mostraram-se eficientes na eletrooxidação do metanol em todas as concentrações e podem ser utilizados em substituição à platina lisa, pois, aumentaram o número de sítios ativos disponíveis mesmo nas menores concentrações investigadas. Esta área superficial de platina disponível nos eletrodos modificados foi calculada pela diferença das integrais do primeiro e segundo ciclos durante processo de varredura cíclica nas medidas de CO adsorvido considerando-se uma carga de platina lisa de 484μC.cm2.

Submitted by (lucia.rodrigues@ufrpe.br) on 2017-02-16T13:10:45Z No. of bitstreams: 1 Romulo Augusto Lins de Campos.pdf: 5930168 bytes, checksum: 7553330ff526456aa81970434c7c3475 (MD5) / Made available in DSpace on 2017-02-16T13:10:45Z (GMT). No. of bitstreams: 1 Romulo Augusto Lins de Campos.pdf: 5930168 bytes, checksum: 7553330ff526456aa81970434c7c3475 (MD5) Previous issue date: 2011-03-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Potentiometric sensors are known for their high sensitivity and selectivity. Such sensors have versatility, low cost and robustness, which ensures their applicability in a wide variety of complex chemical samples. The ion-selective electrodes for polymeric membrane are the best known potentiometric sensors, has by these traits. However, modified carbon paste electrodes have gained prominence due a great advance in their studies. This paper proposes an electrode chemically modified carbon paste for potentiometric determination of copper (II), using a new ionophore lariat-crown ether synthesized from precursor aminopropyl triethoxysilane is a silylating agent known in the literature. Studies were conducted to evaluate the influence of pH on the potential, the best buffer as supporting electrolyte, and the experimental design of mixtures to obtain the best composition of EQMPC. The proposed electrode showed a sensitivity of 38.5 mV/decade of activity with a detection limit of 2.04 x 10-5 mol L-1, and as a supporting electrolyte buffer biftalate/HCl pH = 3.0 proving to be promising for application in the determination of Cu(II). The electrode showed no significant analytical sensitivity to Co(II), Ni(II) and Zn(II) being these their main interferences. / Sensores potenciométricos são conhecidos por sua alta sensibilidade e seletividade. Tais sensores apresentam versatilidade, baixo custo e robustez, o que garante a esses sensores aplicabilidade em uma grande variedade de amostras químicas complexas. Os eletrodos íon-seletivos de membrana polimérica são os sensores potenciométricos mais conhecidos, por possuirem essas características. Contudo, os eletrodos modificados de pasta de carbono têm ganhado forte destaque devido ao avanço em seus estudos. Neste trabalho é proposto um eletrodo quimicamente modificado de pasta de carbono para determinação potenciométrica de cobre (II), utilizando um novo ionóforo lariat-éter coroa sintetizado a partir de precursor aminopropil trietoxisilano que é um agente sililante conhecido na literatura. Foram realizados estudos para avaliar a influência do pH sobre o potencial, o melhor tampão como eletrólito de suporte, além do planejamento experimental de misturas para se obter a melhor composição do EQMPC. O eletrodo proposto apresentou uma sensibilidade de 38,5mV/década de atividade com limite de detecção de 2,04 x 10-5 mol L-1, tendo como eletrólito de suporte um solução-tampão biftalato/HCl pH = 3,0 demonstrando ser promissor para aplicação na determinação de íons Cu(II). O eletrodo não apresentou sensibilidade analítica significativa aos íons Co(II), Ni(II) e Zn(II) sendo esses seus principais interferentes.

Metal ion contamination in surface and ground water is a major threat as it has a direct implication on the health of terrestrial and aquatic flora and fauna. Lead (Pb2+), mercury (Hg2+), cadmium (Cd2+), nickel (Ni2+), copper (Cu2+) and cobalt (Co2+) are few of these metal ions which are classified under the high risk category. Of these, lead and mercury are of greater concern, as even nanomolar concentrations can be lethal, as they can be bio-accumulated and result in physiological as well as neurological disorders. In Asian countries like India and China, heavy metal pollution is more prevalent, as a consequence of poor governmental policies or ineffective or inadequate measures to combat this problem. In recent times, the monitoring and assessment of water pollution is a critical area of study, as it has a direct implication for its prevention and control. The major techniques used for metal ion detection are atomic absorption spectroscopy (AAS), X-ray fluorescence, ion chromatography, neutron activation, etc. Alternatively, the electrochemical, optical and electrical methods provide a platform for the fabrication of portable devices, which can facilitate the on-site analysis of samples in a rapid and cost-effective manner. This has led to a new field of research called chemical sensors or chemo sensory devices. The main aim of this study is to develop various chemosensory materials and test their response towards metal ion sensing. In this study, electroactive polymers have been synthesized for various sensor applications. The focus has been to design synthesize and test various functionalized electroactive polymers (FEAP) for the development of electrochemical, optical and chemoresistive sensors. Electroactive polymers like polyaniline, polypyrrole, polypyrrole grafted to exfoliated graphite oxide and dipyrromethene conjugated with p-(phenylene vinylene) have been synthesized and evaluated after functionalizing with metal coordinating ligands. These metal coordinating ligands were selected, in order to enhance their metal uptake capacity. Various metal ligands like imidazole, tertiary amine group, iminodiacetic acid, and dipyrromethene incorporated either in the polymer backbone or as a part of the backbone have been chosen for the metal binding. These functionalized electroactive polymers (FEAP) served as active material for metal ion sensing. The present investigation is subdivided into three sections. The first part includes design and chemical synthesis of the functionalized polymers by a series of organic reactions. The synthesis has been followed up by characterization using spectroscopic methods including NMR, FTIR, GCMS and Mass spectrometry. In the second part of the investigation, the synthesized polymer has been characterized for the changes in electronic, electric and optical properties after interaction with the selected metal ions. For this, the FEAP is allowed to interact with various metal ions and the changes in the relevant properties have been measured. This includes the study of changes in the conductivity, electronic properties like absorption or emission of the polymer, changes in the redox properties, etc. The third phase of investigation deals with the fabrication of the devices using the active FEAP. The sensor devices comprised of either films, or electrode modified with FEAP or solution of the FEAP, in combination with an appropriate technique has been used for the sensing. The major objectives are enumerated below 1. Functionalzation of polyaniline with imidazole functional group to get imidazole functionalized polyaniline (IMPANI) and study of the electronic, electrical and optical properties of the same. 2. Preparation of films of IMPANI and study of the change in conductivity of the film upon interaction with various metal ions, namely Cu2+, Co2+ and Ni2+ in their chloride form. 3. Synthesis of amine functionalized aniline monomer and chemical graft polymerization onto exfoliated graphite oxide as a substrate to synthesise the amine funtionalised polyaniline grafted to exfoliated graphite oxide (EGAMPANI). Modification of the carbon paste electrode (CPE) with EGAMPANI and study of the electrode characteristic. 4. Study of the electrode properties of EGAMPANI modified carbon paste electrode. 5. Evaluation of the EGAMPANI modified carbon paste electrode as a multi-elemental voltammetric sensor for Pb2+, Hg2+ and Cd2+ in aqueous system. 6. Functionalization of polypyrrole with iminodiacetic acid and characterization of the polymer to synthesis iminodiacetic acid functionalized polypyrrole (IDA-PPy). 7. Modification of the CPE with IDA-PPy by drop casting method and evaluation of the Pb2+ sensing properties. 8. Study of the effect of other metal ions say Hg2+, Co2+, Ni2+, Zn2+, Cu2+ and Cd2+ on the anodic stripping current of Pb2+ using EGAMPANI modified CPE. 9. Synthesis of dipyrromethene-p-(phenylene vinylene) conjugated polymer for heavy metal ion sensing. 10. Study of the changes in the optical absorption and emission properties of the polymer in THF and evaluation of the change in these optical properties upon interaction with the metal ions as analyte. The salient findings of the research work are highlighted as follows, In the first synthesis, aniline has been functionalized with imidazole group and this monomer has been chemical oxidatively polymerized to obtain imidazole functionalized polyaniline (IMPANI). The synthesized polymer possesses a nano-spherical structure, as confirmed from the morphological characterisation using scanning electron microscopy. The IMPANI has been interacted with a representative metal ion, copper (II) chloride, and the copper complexed polymer (Cu-IMPANI) has been subjected to various studies. The coordination of copper with IMPANI results in an increase of molecular weight of the polymer as a result of aggregation, as observed from dynamic light scattering measurements. Apart from this, a significant finding is the decrease of the pH of the system after copper ion coordination attesting to the generation of a secondary hydrochloride ion during the coordination of the copper to the imidazole side chain. This is further confirmed by an increase in conductivity of the Cu-IMPANI compared to IMPANI, measured using the four-probe technique. The increase of conductivity due to copper coordination is one order of magnitude higher. The films which have been prepared from IMPANI and Cu-IMPANI exhibit different morphology. The Cu-IMPANI film prepared by prior co-ordination of Cu ion with IMPANI powder shows a flaky structure, which is not preferable for the conductivity measurements, as a consequence of discontinuity in the medium. To overcome this problem, IMPANI films were initially prepared and then interacted with copper ions for a desired duration, before measurement of the conductivity. This latter procedure enabled the preparation of smooth films for the development of chemoresistive sensors. In continuation of the initial study highlighted above, IMPANI films of thickness 0.02 ± 0.001 mm have been prepared using IMPANI and PANI in DMPU in the ratio of 7:3 by mass. After exposure of the films with respective metal chlorides, such as Ni2+, Co2+ and Cu2+, a change in conductivity is observed in the concentration range of 10-2 to 1 M of metal chlorides. The sensor response may be arranged in the sequence: Ni2+ > Cu2+ > Co2+ at 1M concentration. On the contrary, films prepared from PANI-EB under identical conditions do not exhibit any appreciable change in conductivity. The optimum exposure time is determined to be 10 min for a maximum change in conductivity, after exposure to the chosen metal ions. In the second system taken up for investigation, a tertiary amine containing polyaniline (AMPANI) has been grafted to exfoliated graphite oxide. The amine containing polyaniline grafted to exfoliated graphite oxide (EGAMPANI) has been characterised for structural, morphological and elemental composition. The grafting percentage has been determined to be 7 % by weight of AMPANI on the EGO surface. The synthesized EGAMPANI (5 weight %) has been used to modify carbon paste electrode (CPE) for electrochemical sensor studies. Based on the differential pulse anodic stripping voltammetric studies, the electrochemical response may be arranged in the following sequence: Pb 2+>Cd 2+>Hg 2+ The minimum detection levels obtained are 5×10-6, 5×10-7, and 1.0×10-7 M for Hg2+, Cd2+ and Pb2+ ions respectively. In the next study, an iminodiacetic acid functionalized polypyrrole (IDA-PPy) has been synthesized and characterised for its elemental and structural properties. This has been further used to modify the CPE by drop casting method and used for the specific detection of Pb2+ in acetate buffer. Various parameters governing the electrode performance such as concentration of depositing solution, pH of depositing solution, deposition potential, deposition time, and scan rate, have been optimized to achieve maximum performance and found to be 20 μl, 4.5, -1.3 V, 11 min, 8 mV s-1 respectively for the chosen parameters. Additionally, the influence of other heavy metal ions on the lead response has been studied and it is observed that Co, Cu and Cd ions are found to be interfering. Further, the response of Cd, Co, Cu, Hg, Ni and Zn on IDA-PPy functionalized electrode has been evaluated. The selectivity of IDA-PPy modified electrode for Pb2+ is observed in the concentration range of 1 × 10-7 M and below. The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentration in the range from 1×10-6 to 5×10-9 M and with a lowest limit of detection (LLOD) of 9.6×10-9 M concentration. The efficacy of the electrode for lead sensing has also been evaluated with an industrial effluent sample obtained from a lead battery manufacturing unit. The fourth synthesis pertained to the development of an optical sensor for Fe2+, and Co2+ ions. For this, dipyrromethene as a metal coordinating ligand in conjugation with p-phenylenevinylene has been synthesized and tested for its structural as well as optical properties. It is observed that the polymer shows three absorptions, namely at 294 nm, 357 nm and a major absorption observed as a broad band ranging from 484 to 670 nm. The emission spectrum of the polymer excited at 357 nm shows a characteristic blue emission with a maximum intensity centered at 425 nm. The emission quenching in the presence of various metal ions have been tested and are found to be quenched in presence of Fe2+ and Co2+ ions. All the other metal ions tested namely, Cr3+, Cu2+, and Zn2+ are not found to exhibit any change in the emission spectra below the concentration of 1 × 10-4 M. The linear correlation of the emission intensity with the concentration of the Co2+ and Fe2+ ions has been determined using Stern-Volmer plot. For Co2+ the Stern-Volmer regime is observed from 1×10-4 to 9×10-4 M concentration and the quenching constant Ksv is determined to be 8.67 ×103 M-1. For Fe2+, the linearity is found to be in the regime of 1×10-5 to 9×10-5 M and the quenching constant Ksv is determined to be 7.90 × 103 M-1. In conclusion, different electroactive polymers functionalized with metal coordinating ligands have been synthesized, characterised and evaluated for metal sensing applications. Techniques like electrochemical, optical and conductivity have been used to characterise the response of these FEAP towards metal sensing. It is can be concluded that the electrochemical sensors are more reliable for sensing especially at very low concentrations of metal ions such as Pb, Cd and other techniques like optical and conductimetric are good for detecting metal ions namely Fe, Co, Ni, Cu. The selectivity towards the metal ions is a function of the metal chelating ligand and the extent of sensitivity is dependent upon the technique employed.