O presente trabalho descreve o uso de eletrodos de carbono vítreo como eletrodo-base para modificação com hexacianoferratos de Fe (FeHCF), Co (CoHCF) e Ni (NiHCF) por meio da adsorção destes complexos utilizando a técnica de voltametria cíclica. Os eletrodos quimicamente modificados (EQMs) preparados por este método apresentam características diferenciadas tais como robustez e estabilidade ao longo das medidas eletroquímicas, além de boas propriedades redox. Os EQMs com FeHCF e NiHCF foram avaliados em função da sua atividade eletrocatalítica para a reação de oxidação do Ácido Ascórbico em solução de KCl 0,1 mol L-1 (pH 6,6). O EQM com CoHCF foi avaliado nas mesmas condições dos outros filmes, porém não apresentou uma diminuição no sobrepotencial de oxidação do Ácido Ascórbico. Embora não tenha apresentado uma resposta semelhante aos EQMs com FeHCF e NiHCF, o EQM com CoHCF apresentou a melhor sensibilidade da resposta de corrente de pico quando comparado aos demais. A fim de proporcionar a renovação da superfície do eletrodo foi avaliada a utilização de eletrodos de pasta de carbono modificada com FeHCF, CoHCF ou NiHCF. Os parâmetros de composição da pasta, o eletrólito suporte e o pH foram avaliados utilizando o EPCM com FeHCF por meio da técnica de voltametria cíclica e os parâmetros otimizados foram aplicados no uso dos EPCM com CoHCF e NiHCF. Para avaliar a sensibilidade na deteccção da L-Cisteína, do Glifosato e da N-Acetilcisteína, os EPCMs modificados foram submetidos a estudos com a técnica de voltametria de onda quadrada. Todos os analitos apresentaram resposta eletroquímica em todos os EPCMs, porém as melhores respostas foram para o FeHCF na presença de L-Cisteína, CoHCF na presença de Glifosato e NiHCF na presença de N-Acetilcisteína. Na presença de 1 x 10-8 mol L-1 dos analitos os EPCMs com hexacianoferratos apresentaram um boa resposta eletroquímica, embora não tenha sido possível observar uma linearidade entre o aumento da concentração dos analitos propostos e a corrente de pico. Essa sensibilidade demonstrada pelos EPCMs na presença de moléculas com grupos funcionais, como ácidos carboxílicos, aminoácidos e tióis abre novas perspectivas para a análise direta de compostos de interesse clínico, farmacêutico e amostras de interesse ambiental. / This work describes the use of glassy carbon electrodes as the base for electrode modification with hexacyanoferrates of Fe (FeHCF), Co (CoHCF) and Ni (NiHCF) through adsorption of these complexes using cyclic voltammetry. The chemically modified electrodes (CMEs) prepared by this method have specific features such as robustness and stability along the electrochemical measurements, and good redox properties. The CME with FeHCF and NiHCF were evaluated take into accounting their electrocatalytic activity for oxidation reaction of Ascorbic Acid in KCl 0.1 mol L-1 (pH 6.6). The CME with CoHCF was evaluated under the same conditions, but did not show a decrease on the overpotential for Ascorbic Acid oxidation. Although the CME with CoHCF has not showed the same behavior presented by CMEs with FeHCF and NiHCF, the CME with CoHCF presented the best sensitivity in order to relationship between peak current and concentration of Ascorbic Acid when compared to CMEs with either. In order to provide the renewal of the electrode surface was evaluated the use of carbon paste electrodes (CPEs) modified with FeHCF, CoHCF and NiHCF. The CPE parameters such as composition, supporting electrolyte and pH were evaluated using the CPE with FeHCF by cyclic voltammetry and these optimized parameters were applied for CPEs with CoHCF and NiHCF. The studies about the sensitivity of the detection for L-Cysteine, glyphosate and N-acetylcysteine using the modified CPEs with hexacyanoferrates were performed by square wave voltammetry. All analytes showed electrochemical response at all CPEs, but the best electrochemical responses were obtained for FeHCF in the presence of L-Cysteine, CoHCF in the presence of glyphosate and NiHCF in the presence of N-acetylcysteine. The CPEs with hexacyanoferrates in the presence of 1 x 10-8 mol L-1 of L-Cysteine, glyphosate or N-acetylcysteine had showed a good electrochemical response, although were not possible to observe a linear correlation between the concentration of analytes and peak current. This sensitivity demonstrated by CPEs with hexacyanoferrates electrodes in presence of specific functional groups such as carboxylic acids, amino acids and thiols opens new perspectives for the direct analysis of compounds with clinical, pharmaceutical and environmental samples.

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<p>Cilj ove doktorske disertacija&nbsp; bio je razvoj&nbsp; novih, osetljivih, selektivnih i ekonomski<br />isplativih&nbsp; voltametrijskih&nbsp; radnih&nbsp; elektroda&nbsp; za&nbsp; praćenje&nbsp; odabranih&nbsp; analita&nbsp; kako&nbsp; u<br />laboratorijskim tako i pri terenskim uslovima.&nbsp; Ispitivana je&nbsp; mogućnost primene&nbsp; ovih&nbsp; radnih&nbsp; elektroda&nbsp; primenom&nbsp; voltametrijskih&nbsp; metoda&nbsp; kako&nbsp; u&nbsp; model&nbsp; rastvorima&nbsp; tako&nbsp; i&nbsp; u&nbsp; pojedinim realnim sistemima. SW-ASV&nbsp; zasnovana&nbsp; na&nbsp; elektrodama&nbsp; od&nbsp; staklastog&nbsp; ugljenika&nbsp; povr&scaron;inski modifikovanim&nbsp; Bi-MWCNT&nbsp; i&nbsp; BiOCl-MWCNT&nbsp; je&nbsp; primenjena&nbsp; za&nbsp; određivanje&nbsp; jona&nbsp; Pb(II)&nbsp; i Cd(II)&nbsp; pri&nbsp; optimizovanim&nbsp; uslovima&nbsp; merenja.&nbsp; Određivanje&nbsp; ciljnih&nbsp; jona&nbsp; vr&scaron;eno&nbsp; je&nbsp; pri&nbsp; radnom potencijalu&nbsp; od&nbsp; -1,2&nbsp; V&nbsp; (izmeren&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; zasićenu&nbsp; kalomelovu&nbsp; elektrodu)&nbsp; i&nbsp; vremenu<br />elektrodepozicije jona&nbsp; od 120 s. Sva merenja su izvr&scaron;ena u rastvoru acetatnog pufera čija je pH-vrednost iznosila&nbsp; 4,0. Primenjeni koncentracioni opseg ciljnih analita iznosio je&nbsp; od 5 do 50&nbsp; &mu;g&nbsp; dm ^-3 .&nbsp; Primenom&nbsp; ovog&nbsp; tipa&nbsp; elektrode&nbsp; dobijene&nbsp; su&nbsp; vrednosti&nbsp; granice&nbsp; detekcije&nbsp; za&nbsp; jone Pb(II) i Cd(II) 0,57&nbsp; &mu;g dm ^-3i 1,2 &mu;g dm^-3 , redom. Dobijena RSD iznosila je manje od 10% za oba&nbsp; jona.&nbsp; Ova&nbsp; metoda&nbsp; je&nbsp; primenjena&nbsp; i&nbsp; za&nbsp; određivanje&nbsp; ciljnih&nbsp; jona&nbsp; u&nbsp; realnom&nbsp; uzorku&nbsp; porne vode&nbsp; sedimenta&nbsp; a&nbsp; rezultati&nbsp; dobijeni&nbsp; optimizovanom&nbsp; voltametrijskom&nbsp; metodom&nbsp; su&nbsp; u&nbsp; dobroj saglasnosti sa rezultatima koji su dobijeni primenom komparativne GFAAS metode. Bizmut oksihlorid-vi&scaron;ezidne ugljenične nanocevi kompozitni materijal je primenjen za povr&scaron;insko&nbsp; modifikovanje&nbsp; elektrode&nbsp; od&nbsp; staklastog&nbsp; ugljenika&nbsp; za&nbsp; brzo&nbsp; i&nbsp; jednostavno voltametrijsko&nbsp; određivanje&nbsp; tragova&nbsp; Zn(II)-jona&nbsp; primenom&nbsp; SW-ASV&nbsp; metode.&nbsp; BiOClMWCNT/GCE je pokazala linearan analitički odgovor u&nbsp; osegu koncentracija od&nbsp; 2,50 do&nbsp; 80,0 &mu;g&nbsp; dm ^-3sa dobijenom vredno&scaron;ću GD 0,75 &mu;g&nbsp; dm^-3pri akumulacionom vremenu od&nbsp; 120 s&nbsp; i potencijalu&nbsp; elektrodepozicije&nbsp; -1,40&nbsp; V&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; ZKE.&nbsp; Merenja&nbsp; su&nbsp; vr&scaron;ena&nbsp; u&nbsp; acetatnom puferu pH 4,5. Dobijena RSD iznosila je 4,8 %. Upoređene su performanse novodizajnirane BiOCl-MWCNT/GCE elektrode&nbsp; i&nbsp; tradicionalne elektrode na bazi bizmut filma (BiF/GCE), MWCNT/GCE,&nbsp; BiF-MWCNT/GCE&nbsp; i&nbsp; nemodifikovane&nbsp; GC&nbsp; elektrode.&nbsp; Novodizajnirana elektroda je primenjena za&nbsp; detekciju&nbsp; i određivanje&nbsp; Zn(II)-jona&nbsp; u realnim&nbsp; uzorcima kao &scaron;to su<br />dijetetski&nbsp; suplement&nbsp; i&nbsp; pekarski&nbsp; kvasac.&nbsp; Dobijeni&nbsp; rezultati&nbsp; su&nbsp; uporedivi&nbsp; sa&nbsp; deklarisanom vredno&scaron;ću&nbsp; u&nbsp; slučaju&nbsp; dijetetskog&nbsp; suplementa&nbsp; a&nbsp; u&nbsp; slučaju&nbsp; pekarskog&nbsp; kvasca&nbsp; sa&nbsp; rezultatima dobijenih komparativnom FAAS .<br />Elektroda od ugljenične paste je povr&scaron;inski modifikovana pripremljenim kompozitom<br />koji je&nbsp; izgrađen od vi&scaron;ezidnih ugljeničnih nanocevi i čestica&nbsp; Sb₂O_3.&nbsp; Kompozitni&nbsp; materijal&nbsp; je okarakterisan&nbsp; primenom&nbsp; TEM,&nbsp; EDS&nbsp; i&nbsp; XRD&nbsp; mernih&nbsp; tehnika.&nbsp; Sb₂O₃-MWCNT/CPE&nbsp; je okarakterisana primenom ciklične voltametrije a merenja su vr&scaron;ena u rastvoru hlorovodonične kiseline&nbsp; (pH&nbsp; 2,0).&nbsp; Primenom&nbsp; SW-ASV&nbsp; metode&nbsp; ova&nbsp; radna&nbsp; elektroda&nbsp; je&nbsp; upotrebljena&nbsp; za određivanje&nbsp; jona Pb(II) i Cd(II)&nbsp; u&nbsp; koncentracionom opsegu 2,0-40,0&nbsp; &mu;g&nbsp; dm&nbsp; ^-3za&nbsp; Pb(II)-jon&nbsp; i 2,0-40,0&nbsp; &mu;g&nbsp; dm ^-3 za&nbsp; Cd(II)-jon&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijene&nbsp; dobre&nbsp; linearne&nbsp; zavisnosti&nbsp; za&nbsp; oba&nbsp; ciljna jona.&nbsp; Optimalna&nbsp; procedura&nbsp; uključuje&nbsp; primenu&nbsp; Sb2O3-MWCNT/CPE&nbsp; u&nbsp; 0,01&nbsp; mol dm ^-3<br />hlorovodoničnoj kiselini uz vreme elektrodepozicije jona iz rastvora od 120&nbsp; s&nbsp; na&nbsp; potencijaluod&nbsp; -1,2&nbsp; V,&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijene&nbsp; vrednosti&nbsp; za&nbsp; GD&nbsp; 1,1&nbsp; &mu;g&nbsp; dm ^-3 Cd(II)&nbsp; i&nbsp; 1,6&nbsp; &mu;g&nbsp; dm ^-3 Pb(II). Optimizovana&nbsp; metoda&nbsp; zasnovana&nbsp; na&nbsp; ovom&nbsp; tipu&nbsp; voltametrijskog&nbsp; senzora&nbsp; je&nbsp; uspe&scaron;no primenjena&nbsp; za&nbsp; određivanje&nbsp; jona&nbsp; Cd(II)&nbsp; u&nbsp; obogaćenom&nbsp; uzorku&nbsp; česmenske&nbsp; vode,&nbsp; gde&nbsp; su&nbsp; se dobijene vrednosti u&nbsp; saglasnosti sa očekivanom. Elektroda od ugljenične paste povr&scaron;inski je&nbsp; modifikovana primenom&nbsp; Sb₂O₃-MWCNT nanokompozitnog&nbsp; materijala&nbsp; i&nbsp; primenjena&nbsp; za&nbsp; direktno&nbsp; voltametrijsko&nbsp; određivanje imidakloprida&nbsp; u&nbsp; model&nbsp; rastvorima.&nbsp; U&nbsp; cilju&nbsp; postizanja&nbsp; &scaron;to&nbsp; boljih&nbsp; analitičkih&nbsp; performansi optimizovani su eksperimentalni uslovi merenja kao &scaron;to su pH-vrednost rastvora pomoćnog elektrolita&nbsp; i&nbsp; kondicioniranje&nbsp; povr&scaron;ine&nbsp; voltametrijskog&nbsp; senzora.&nbsp; Kao&nbsp; optimalna&nbsp; pH-vrednost pomoćnog elektolita (Britton-Robinsonovog pufera) odabrana je pH 7,0, a ponavljanje ciklusa cikliranja najmanje 4 puta povoljno utiče na stabilnost&nbsp; voltametrijskih signala. Optimizovana metoda primenjena je za SW direktno katodno određivanje imidakloprida u koncentracionom intervalu od 1,41 do 32,77 &mu;g cm ^-3 uz dobijeni korelacioni faktor od 0,9995. Na osnovu dobijenih rezultata može se zaključiti da su razvijene analitičke metode pre svega&nbsp; osetljive,&nbsp; selektivne,&nbsp; reproduktivne&nbsp; i&nbsp;&nbsp; jednostavne&nbsp; &scaron;to&nbsp; omogućava&nbsp; njihovu&nbsp; primenu&nbsp; za veliki broj uzoraka.&nbsp; Merenjima u model i realnim rastvorima dokazana je mogućnost njihove primene&nbsp; u&nbsp;&nbsp; komplikovanim&nbsp; matriksima,&nbsp; pri&nbsp; različitim&nbsp; pH&nbsp; vredostima&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijeni<br />rezultati koji su u saglasnosti sa rezultatima primenjenih komparativnih metoda. Naravno, za dobijanje&nbsp; reprezentativnih&nbsp; rezultata&nbsp; neohodno&nbsp; je&nbsp; izvr&scaron;iti&nbsp; optimizaciju&nbsp; uslova&nbsp; merenja&nbsp; &scaron;to podrazumeva sam odabir supstrat-elektrode, odabir povr&scaron;inskog modifikatora i optimizaciju eksperimentalnih uslova merenja.</p> / <p>The&nbsp; aim of this&nbsp; Ph.D. thesis&nbsp; was the development of new, sensitive, selective and economically&nbsp; viable&nbsp; voltametric&nbsp; working&nbsp; electrode&nbsp; for&nbsp; continuous&nbsp; monitoring&nbsp; of&nbsp; different target&nbsp; analytes.&nbsp; The&nbsp; use&nbsp; of&nbsp; these&nbsp; advantaged&nbsp; working&nbsp; electrodes&nbsp; was&nbsp; investigated&nbsp; using voltametric methods both in model solutions and in certain real systems.SW-ASV&nbsp; based on glassy carbon&nbsp; electrode surface modified with&nbsp; Bi- MWCNT and BiOCl-MWCNT&nbsp; were&nbsp; applied&nbsp; for&nbsp; determination&nbsp; of&nbsp; Pb(II)&nbsp; and&nbsp; Cd(II)&nbsp; ions.&nbsp; Voltametric determination&nbsp; of&nbsp; Pb(II)&nbsp; and&nbsp; Cd(II)&nbsp; ions&nbsp; was&nbsp; performed&nbsp; at&nbsp; working&nbsp; potential&nbsp; of&nbsp; -1.2&nbsp; V (measured against the saturated calomel electrode) and time of electrodeposition of 120 s. All measurements were performed in acetate buffer solution pH 4.0. Concentration range of targetanalites were&nbsp; 5-50 &mu;g&nbsp; dm -3 . Using this type of electrode,&nbsp; obtained&nbsp; detection limits for&nbsp; Pb(II) and Cd(II) ions&nbsp; were&nbsp; 0.57&nbsp; &mu;g&nbsp; dm -3 and 1.2&nbsp; &mu;g&nbsp; dm -3 , respectively, with RSD lower than 10%.This&nbsp; method&nbsp; was&nbsp; applied&nbsp; for&nbsp; target&nbsp; ions&nbsp; determination&nbsp; in&nbsp; sediment&nbsp; pore&nbsp; water&nbsp; sample,&nbsp; and obtained results are comparable with those who are obtained using GFAAS method. Bismuth oxychloride-multiwalled carbon nanotubes composite material was applied for&nbsp; surface&nbsp; modification&nbsp; of&nbsp; the&nbsp; glass-carbon&nbsp; electrode&nbsp; for&nbsp; quick&nbsp; and&nbsp; simple&nbsp; voltametric determination&nbsp; of&nbsp; Zn(II)&nbsp; ions&nbsp; using&nbsp; the&nbsp; SW-ASV&nbsp; method.&nbsp; BiOCl-MWCNT/GCE&nbsp; showed&nbsp; a linear&nbsp; analytical&nbsp; response&nbsp; in&nbsp; a&nbsp;&nbsp; concentration&nbsp; from&nbsp; 2.50&nbsp; to&nbsp; 80.0&nbsp; &mu;g&nbsp; dm -3 with&nbsp; a&nbsp; value&nbsp; of detection limit 0.75 &mu;g dm -3 at a acumulation time of 120 s and an electrodeposition potential of&nbsp; -1.40 V vs. saturated&nbsp; calomel electrode.&nbsp; Measurements were carried out in acetate buffer pH 4.5. The obtained&nbsp; value of the RSD&nbsp; was&nbsp; 4.8%. The performance of the newly designed BiOCl-MWCNT/GCE&nbsp; electrode,&nbsp; traditional&nbsp; bismuth-based&nbsp; electrode&nbsp; (BiF/GCE), MWCNT/GCE,&nbsp; BiF-MWCNT/GCE&nbsp; and&nbsp; unmodified&nbsp; GC&nbsp; electrodes&nbsp; were&nbsp; compared.&nbsp; The applied electrode shows very good electroanalytic properties when determining this target ion. Obtained results are in good agreement with declared value in case of dietetic suplement, and in the brewer&rsquo;s yeast sample results were comparable with FAAS results. Carbon&nbsp; paste&nbsp; electrode&nbsp; surface&nbsp; modified&nbsp; with&nbsp; new&nbsp; composite&nbsp; material&nbsp; based&nbsp; on multiwalled carbon nanotubes and&nbsp; Sb2O3&nbsp; particles. The composite is characterized by TEM, EDS and&nbsp; XRD measurment. Sb2O3- MWCNT/CPE was characterized by cyclic voltammetry and measurements were carried out in a&nbsp; hydrochloric acid&nbsp; solution&nbsp; (pH 2.0). Using the SWASV&nbsp; method,&nbsp; this&nbsp; working&nbsp; electrode&nbsp; was&nbsp; used&nbsp; to&nbsp; determine&nbsp; Pb(II),&nbsp; Cd(II)&nbsp; ions&nbsp; in&nbsp; the concentration range&nbsp; from&nbsp; 2.0&nbsp; to 40.0&nbsp; &mu;g dm -3 for Pb(II) and 2.0-40.0&nbsp; &mu;g dm -3 for Cd(II) ions. Newly&nbsp; designed&nbsp; sensor&nbsp; showed&nbsp; good&nbsp; linear&nbsp; dependences&nbsp; for&nbsp; both&nbsp; target&nbsp; ions.&nbsp; The&nbsp; most optimal&nbsp; procedure&nbsp; involving&nbsp; application&nbsp; of&nbsp; Sb2O3-MWCNT/CPE&nbsp; in&nbsp;&nbsp; .01&nbsp; mol&nbsp; dm -3 hydrochloric&nbsp; acid,&nbsp; with&nbsp; electroposition&nbsp; time&nbsp; of&nbsp; target&nbsp; ions&nbsp; 120&nbsp; s&nbsp; at&nbsp; a&nbsp; electrodeposition potential&nbsp; of&nbsp; -1.2&nbsp; V.&nbsp; Obtained&nbsp;&nbsp; values&nbsp; of&nbsp;&nbsp;&nbsp; LOD&nbsp; 1,1&nbsp; &mu;g&nbsp; dm -3 for&nbsp; Cd(II)&nbsp; and&nbsp; for&nbsp; 1,6&nbsp; &mu;g&nbsp; dm -3 Pb(II)&nbsp; ions.&nbsp; An&nbsp; optimized&nbsp; method&nbsp; based&nbsp; on&nbsp; this&nbsp; type&nbsp; of&nbsp; voltametric&nbsp; sensor&nbsp; has&nbsp; been successfully&nbsp; applied&nbsp; for&nbsp; determination&nbsp; of&nbsp; Cd(II)&nbsp; ion&nbsp; in&nbsp; a&nbsp; spiked&nbsp; tap&nbsp; water&nbsp; sample.&nbsp; Results obtained during this measurment were in tune with expected results. CPE&nbsp; was&nbsp; surface&nbsp; modified&nbsp; using&nbsp; Sb2O3-MWCNT&nbsp; nanocomposite&nbsp; material&nbsp; and tested&nbsp; for&nbsp; direct&nbsp; voltametric&nbsp; determination&nbsp; of&nbsp; imidacloprid&nbsp; in&nbsp; model&nbsp; solutions.&nbsp; In&nbsp; order&nbsp; to achieve the best analytical performance, experimental conditions of measurement such as the pH value of the supporting electrolyte and conditioning of the voltametric sensor surface havebeen&nbsp; optimized.&nbsp; As&nbsp; an&nbsp; optimum&nbsp; pH&nbsp; value&nbsp; of&nbsp; the&nbsp; supporting&nbsp; electrolyte&nbsp; (Britton-Robinson buffer), a pH 7.0 was selected, and the repeating cycles of the cycling process at least 4 times favorably&nbsp; influenced&nbsp; the&nbsp; stability&nbsp; of&nbsp; the&nbsp; voltametric&nbsp; signals.&nbsp; The&nbsp; optimized&nbsp; method&nbsp; was applied for the SW direct cathodic determination&nbsp; of&nbsp; imidacloprid in the concentration range from 1.41 to 32.77 &mu;g cm -3&nbsp; with obtained correlation factor of 0.9995. Based on results it can be concluded that developed analytical methods are sensitive, selective, reproducibile and simple, which can enable their application for various number of samples. Measurements in the model and real solutions have demonstrated the possibility of their&nbsp; application&nbsp; in&nbsp; complicated&nbsp; matrices,&nbsp; at&nbsp; different&nbsp; pH,&nbsp; whereby&nbsp; obtained&nbsp; results&nbsp; are&nbsp; in accordance&nbsp; with&nbsp; the&nbsp; results&nbsp; of&nbsp; the&nbsp; applied&nbsp; comparative&nbsp; methods.&nbsp; For&nbsp; obtainig&nbsp; of representative&nbsp; results&nbsp; it&nbsp; is&nbsp; necessary&nbsp; to&nbsp; optimize&nbsp; conditions&nbsp; of&nbsp; measurment&nbsp; which&nbsp; include: selection of substrat electrode, surface modifier and optimization of experimental condition.</p>