Academic literature on the topic 'Glassy carbon paste electrode'

This work is focused on the homemade screen-printed carbon paste electrode containing basically graphite powder (or glassy carbon powder), poly(vinylbchloride) (PVC) and paraffin oil. It compares the electrochemical properties of conventional carbon-based electrodes and prepared screen-printed carbon paste electrodes towards [Fe(CN)6]3-/[Fe(CN)6]4- and quinone/hydroquinone redox couples. Significant attention is paid to the development of the corresponding carbon inks, printing and the surface characterisation of the resulting electrodes by the scanning electron microscopy. An optimization consisted of the selection of the organic solvent, the optimal content of the used polymer with the chosen paste binder, appropriate isolation of electric contact, etc. Very similar properties of the prepared screen-printed electrodes, containing only corresponding carbon powder and 3 % PVC, with their conventional carbon paste electrode and glassy carbon-based electrodes, were observed during their characterisation. Screen-printed electrodes, with the pasting liquid usually provided satisfactory analytical data. Moreover, they can be used in the flow injection analysis and could undoubtedly replace the carbon paste grooved electrodes. It can be assumed that certain progress in the development of electrode materials was achieved by this research.

The possibility of determination of chloramphenicol by differential pulse voltammetry at four different carbon paste electrodes, in the full pH range (2–12) of Britton–Robinson (BR) buffer was investigated. Electrodes were prepared by mixing spectroscopic graphite powder or glassy carbon microbeads with mineral oil (Nujol) or tricresyl phosphate. Under optimal conditions (BR buffer pH 12, the electrode prepared from glassy carbon microbeads and tricresyl phosphate), linear calibration graph was obtained only in 10–5 M chloramphenicol concentration range. Determination of lower concentrations of chloramphenicol was complicated by irreproducible peak of oxygen from the carbon paste which overlapped with peak of chloramphenicol. Addition of sodium sulfite removed the oxygen peak without influence on the peak of chloramphenicol. Under optimal conditions (electrode paste made from glassy carbon microbeads, BR buffer pH 10 and 0.5 M sodium sulfite), straight calibration line was obtained in the 10–6 and 10–5 M chloramphenicol concentration range. Limit of determination was 5 × 10–7 mol/l.

Voltammetry is the general term for all techniques in which the current is measured as a function of electrode potential. The voltammetric techniques can be applied for the quantitative analysis of inorganic and organic species and are best suited for substances which can be either oxidized or reduced on electrodes. These techniques are characterized by high sensitivity which results in the possibility of performing determinations at a low concentration level. In voltammetry, many different types of working electrodes are applied. One of the important groups are solid electrodes, among which carbon electrodes play an important role. They represent a good alternative to mercury electrodes, however, surface preparation before the usage is required. In this work anethole determination will be presented using three types of carbon electrodes: glassy carbon electrode, boron doped diamond electrode and carbon paste electrode. Optimization process will be also described.

The electrochemical behavior of a hypoglycemic drug, glimepiride (GM), was studied at glassy carbon (GCE) and carbon paste (CPE) electrodes in phosphate buffer over the pH range of 2.7–11.7 using cyclic and differential pulse voltammetry. Oxidation of the drug was shown to be an irreversible and diffusion-controlled process. Using differential pulse voltammetry (DPV), the drug yielded a well-defined voltammetric peak in phosphate buffer pH 6.4 at +1.16 V and pH 7.0 at +1.07 V (vs Ag|AgCl) on glassy carbon and carbon paste electrodes, respectively. This process could be used to determine glimepiride concentrations in the range from 1.0 × 10–5 to 3.2 × 10–5 mol l–1 with a detection limit of 2.0 × 10–6 mol l–1 in case of the glassy carbon electrode and in the range of 2.0 × 10–6 to 1.5 × 10–5 mol l–1 with a detection limit of 7.5 × 10–7 mol l–1 in case of the carbon paste electrode. The method was successfully applied to the determination of the drug in a tablet dosage form. Next, the formation of an inclusion complex of glimepiride with β-cyclodextrin (β-CD) in phosphate buffer (pH 7.0):methanol (90:10 (v/v)) has been investigated by differential pulse voltammetry as well as UV spectrophotometry and its stability constant was determined by both methods to be 202.0 and 197.9 l mol–1, respectively.

Background: Nanomaterials have a significant role in improving the performance of electrochemical sensing systems. Unique physical and chemical properties have extended the application of nanomaterials in the fields of engineering, materials and biomedical science. In the last few years, these materials with unique properties have been preferred in the design of experimental approaches for the analysis of metal ions, proteins, biomarkers and pharmaceutical compounds. This paper reports preparation, characterization of two different nanomaterials and their electrochemical application on doublestranded calf-thymus DNA signals. Methods: The multi-walled carbon nanotubes were functionalized with amine groups (MWCNTs-NH2) by employing the dielectric barrier discharge plasma treatment and then applied as MWCNTs- NH2/glassy carbon electrode. Moreover, the synthesized mesoporous silica MCM-41 was chemically amine functionalized and used as MCM-41-NH2/carbon paste electrode. For biosensor preparation, a thin layer of calf thymus double stranded deoxyribonucleic acid (ct-dsDNA) was immobilized over the modified electrodes. Results: The influence of dsDNA immobilized substrate was investigated based on the electrochemical signals. While dsDNA/MCM-41-NH2/carbon paste biosensor showed a selective effect for guanine signals, the dsDNA/MWCNTs-NH2/glassy carbon biosensor presented electrocatalytic effect for dsDNA signals. Both dsDNA modified electrodes were employed to explore the interaction between the dsDNA and the anticancer drug etoposide (ETP) in aqueous solution through voltammetric techniques. By increasing the interaction time with ETP, the adenine peak current was quenched in the presence of MWCNTs-NH2 based glassy carbon electrode. Whereas, in the presence of MCM-41-NH2 based CP electrode, selective interaction with guanine occurred and oxidation peak intensity was diminished. Conclusion: The selective effect of MCM-41-NH2 can be used when the studied substances give a signal with the same potential of adenine.

Carbon paste electrodes containing silicone or paraffin oil as the pasting liquids, preplated with a mercury film, were tested for possible use in potentiometric stripping determination of heavy metals like lead, cadmium and copper. The detailed study has shown that the results are comparable with those obtained with widely used mercury-coated glassy carbon electrode with regard to the linear response at low ppb levels, detection limits, reproducibility, etc. The potentiometric stripping analysis with both electrode materials was used for the determination of lead and copper in a soot sample. No significant differences were found when these results were compared with a reference determination performed by graphite-furnace atomic absorption spectrometry.

The voltammetric behavior of 4-aminobenzoic acid (PABA) and its acetylated metabolite on glassy carbon, carbon fiber or carbon paste electrodes was investigated in an aqueous supporting electrolyte. 4-Aminohippuric acid (4-AHA), 4-acetamidobenzoic acid (4-AMB) and 4-acetamidohippuric acid (4-Ac-AHA) can be separated on a capillary carbon paste electrode in 0.1 M lithium perchlorate. The oxidation potentials of PABA, 4-AHA, 4-AMB and 4-Ac-AHA were 0.70, 0.88, 1.06 and 1.10 V on capillary CPE, respectively. The electrooxidation process is used for simultaneous quantitative determination of acetylated metabolites in urine.

An analytical pesticide assay of O-ethyl-O-4-(nitrophenyl)phenyl phosphonothioate (EPN) was carried out using the following: a carbon nanotube paste electrode, a mercury-immobilized carbon nanotube paste electrode, a glassy carbon electrode, a metal–gold electrode, and a DNA-immobilized carbon nanotube paste electrode (DPE), which is two-fold more sensitive than other sensors. The DPE was optimized using cyclic and square wave stripping voltammetry. Linear working ranges approached 5–55 mg L–1 EPN and the nano-range of 10–210 ng L–1 in a 0.1 mol L–1 NH4H2PO4 electrolyte solution, with a speedy analytical time of 30-s stripping. The detection limit was 2.57 ng L–1 (7.94 × 10–12 mol L–1), and the precision was 0.102% relative standard deviation (n = 15) at the 10.0 mg L–1 EPN spike. This indicates that the method is more sensitive than common voltammetric methods. This method was applied to fruit samples using patch- and needle-type electrodes, specifically on the skin tissues of an orange and an apple. Moreover, the implanted electrode was interfaced with a fish brain cell at the electrochemical workstation. Results showed that the aforementioned method can be used to conduct a pesticide assay in neuro-treated and non-treated cell systems.

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In this work, glassy carbon paste electrodes (GCPE) were modified with porphyran- capped gold nanoparticles (GCPE/AuNps-PFR) and applied for the determination of an anticancer drug, 5-fluorouracil (5-FU), by using differential pulse voltammetry (DPV). The PFR polysaccharide was isolated from commercial Nori seaweed, and its characterization was carried out by FTIR and 13C-NMR as well as by determining its total sugar and sulfate contents, which resulted in 82.8% and 11.9%, respectively. These experiments confirmed the chemical identity and purity of the extracted polysaccharide, which was used as reducing and capping agent to the synthesis of gold nanoparticles (AuNps-PFR). The temperature and the concentrations of AuCl4- and PFR for the AuNps-PFR synthesis were optimized by a 23 full factorial design including a central point assayed in triplicate. The smallest particles were produced with 128.7 nm by employing a temperature of 70 °C and concentrations of 2.5 mmol L-1 for AuCl4- and 0.25 mg mL-1 for PFR. The characterization of the AuNps-PFR nanocomposite was performed by UV-VIS, FTIR and DLS spectroscopies, FESEM, zeta potential and XRD. The UV-VIS spectrum showed an absorption at 524 nm (plasmon band), with no significant changes in its shape and absorption frequency for 90 days. This observation suggests that the AuNps-PFR are stable in suspension, which is in good agreement with the zeta potential of -30.5 mV obtained for the sample. The FTIR spectrum revealed that interactions between the AuNps and the PFR may exist, as a consequence of displacements in the frequency of the bands in the AuNps-PFR spectrum compared to that obtained for the PFR individually. The electrochemical characterization of the porphyran modified GCPE (GCPE/PFR) was carried out by cyclic voltammetry and electrochemical impedance spectroscopy in the presence of the Fe(CN)63-/4- probe, revealing that the polysaccharide had a positive effect on the electrode response, since higher current values and a lower charge transfer resistance for the electrochemical probe redox process were achieved compared to the unmodified GCPE. Even better responses were obtained after the modification of the GCPE with the synthetized AuNps-PFR, as a consequence of the high electrical conductivity and large surface area displayed by the nanocomposite. The 5-FU was oxidized on the GCPE/AuNps-PFR surface according to an irreversible, pH dependent and diffusion controlled mechanism, showing an anodic wave at +1,1 V in BR buffer solution 0.04 mol L-1. The highest current value for 5-FU determination was achieved in BR buffer with pH 8.0, by DPV; therefore, this value was chosen for the further analysis. A linear relationship was observed between the anodic peak potential and the pH of the medium with a slope of -69 mV pH-1, demonstrating that the same number of protons an electrons participate in the 5-FU oxidation mechanism. The GCPE/AuNps-PFR exhibited a linear relationship between the peak current and 5-FU concentration over the range of 29.9 to 234.0 μmol L-1, with low detection (0.66 μmol L-1) and quantification limits (2.22 μmol L-1). Besides the good sensitivity for detecting 5-FU, the modified electrode showed reproducibility, and its response was not influenced by interfering compounds such as glucose, urea, albumin, ascorbic acid, Na+ and K+, suggesting its potential application to determine 5-FU in biologic matrices. The practical utility of the developed sensor was demonstrated for the quantification of 5-FU in pharmaceutical injection sample. A good average recovery percentage of 104.0% was achieved, with an acceptable relative standard deviation of 2.25%. So, these results could confirm the promising analytical performance of the modified electrode for the electroanalysis of 5-FU in real samples.
Neste trabalho, eletrodos de pasta de carbono vítreo (EPCV) foram modificados com nanopartículas de ouro estabilizadas no polissacarídeo sulfatado porfirana (PFR) e aplicados para a determinação do agente antitumoral 5-fluorouracil (5-FU), utilizando voltametria de pulso diferencial (VPD). A PFR foi extraída a partir de alga Nori comercial, e sua caracterização foi realizada por FTIR, RMN-13C e pela determinação dos teores de carboidratos totais e de grupos SO42-, os quais resultaram em 82,8% e 11,9%, respectivamente. Tais experimentos confirmaram a pureza e a identidade química do polissacarídeo extraído, que foi empregado como agente redutor e estabilizante para a síntese de nanopartículas de ouro (AuNps-PFR). A temperatura, a concentração do precursor AuCl4- e a concentração de PFR empregadas para a síntese das AuNps-PFR foram otimizadas por meio de um planejamento fatorial 23 com triplicata no ponto central. Um menor tamanho de partícula (128,7 nm) foi alcançado ao se empregar uma temperatura de 70 °C e concentrações de AuCl4- e PFR iguais a 2,5 mmol L-1 e 0,25 mg mL-1, respectivamente. As AuNps-PFR obtidas foram caracterizadas pelas espectroscopias UV-VIS, FTIR e DLS, MEV-FEG, potencial zeta e DRX. O espectro de UV-VIS mostrou uma banda em 524 nm (banda plasmon), que não apresentou variações significativas na forma e frequência de absorção durante 90 dias. Tais observações sugeriram que as AuNps-PFR são estáveis em suspensão, o que corrobora com o potencial zeta de -30,5 mV obtido para a mesma. O espectro de FTIR evidenciou a existência de interações entre as AuNps e a PFR, devido a deslocamentos das bandas apresentadas no espectro das AuNps-PFR em relação ao obtido para a PFR. A caracterização eletroquímica do EPCV/PFR, realizada por voltametria cíclica (VC) e espectroscopia de impedância eletroquímica em meio da sonda Fe(CN)63-/4-, evidenciou que o polissacarídeo conferiu aos eletrodos maiores valores de corrente e menor resistência à transferência de carga para o processo redox da sonda eletroquímica em comparação aos eletrodos não modificados. Respostas de corrente ainda maiores foram obtidas ao se empregar o EPCV/AuNps-PFR, como uma consequência da elevada condutividade e alta área superficial apresentada pelas nanopartículas. Por VC, verificou-se que o 5-FU foi oxidado irreversivelmente na superfície do EPCV/AuNps-PFR segundo um mecanismo dependente do pH e controlado por difusão, apresentando um processo anódico em +1,1 V em tampão BR 0,04 mol L-1. O pH do tampão BR para a determinação de 5-FU foi otimizado por VPD, tendo-se observado um máximo de corrente em pH 8,0, valor empregado para a obtenção das curvas analíticas. A relação linear observada entre o potencial de pico e o pH do meio com inclinação de -69,0 mV pH-1 evidenciou que o mesmo número de prótons e elétrons estão envolvidos no processo de oxidação. O EPCV/AuNps-PFR apresentou linearidade de resposta na faixa de 29,9 a 234,0 μmol L-1 de 5-FU, com limites de detecção e de quantificação iguais a 0,66 e 2,22 μmol L-1, respectivamente. Além da boa sensibilidade ao 5-FU, o EPCV/AuNps-PFR apresentou reprodutibilidade de resposta, e não sofreu interferência significativa de compostos como glicose, ácido ascórbico, ureia, albumina e íons Na+ e K+, sugerindo sua potencial aplicação para a determinação de 5-FU em matrizes biológicas. O eletrodo modificado foi aplicado para a quantificação do 5-FU em formulação farmacêutica comercial injetável, tendo-se obtido uma porcentagem média de recuperação igual a 104,0, com desvio padrão relativo dentro dos limites aceitáveis (2,25%). Confirma-se, deste modo, o bom desempenho analítico do sensor e da metodologia voltamétrica desenvolvida para a eletroanálise do 5-FU em amostras reais.

Master of Science
Department of Chemistry
Daniel A. Higgins
The potential-dependent reorientation dynamics of double stranded DNA (ds-DNA) covalently attached to planar glassy carbon electrode (GCE) surfaces were studied in this thesis. The orientation of ds-DNA was investigated via the distance-dependent quenching of fluorescence from a 6–carboxyfluorescein (FAM6) flurophore to the electrode surface. The fluorophore was covalently bound to the distal end of the DNA. Fluorescence microscopy was employed for optical detection of FAM6 fluorescence and hence the DNA dynamics. The variation of the fluorescence from the dye with electrode potential is attributed to distance-dependent dipole-electrode energy transfer. Application of positive potentials (i.e., +0.2 V vs. open circuit potential, OCP) to the GCE caused the ds-DNA to align approximately parallel to the surface, yielding strong FAM6-electrode energy transfer and low fluorescence intensity. With the switching of the potential towards negative values (i.e., -0.4 V vs. OCP) the ds-DNA realigned perpendicular to the GCE surface leading to a reduction in energy transfer and high fluorescence intensity. Initial DNA reorientation upon a change in electrode potential is very fast. These fast dynamics have been observed and characterized in a number of previous publications. We have observed subsequent slow dynamics that we attribute to slow orientational relaxation of the DNA. Our observations were first reported by Q. Li, et al., J. Am. Chem. Soc. 2012, 134, 14467. In this thesis, this prior work is extended to verify the reproducibility of these new dynamics and to eliminate the possibility of certain artifacts as their source. Specifically, the experiments are repeated using a new cell design and a different buffer. In the primary experiments performed in this thesis, the dependence of the DNA reorientation dynamics on surface coverage was investigated by observing the fluorescence modulation as a function of probe concentration in the functionalization bath. Concentrations of 0.25, 1.0 and 1.5 µM 35-mer ds-DNA were employed. Electrodes functionalized at these concentrations have ds-DNA surface coverages of 1.18 x 10[superscript]12, 3.24 x 10[superscript]12 and 4.26 x 10[superscript]12 cm[superscript]-2, respectively. With increasing concentration of the DNA probe, the reorientation time constant at positive applied bias (vs. OCP) increased, indicting reorientation was slowed. In contrast, the time constant decreased with the negative applied bias (vs. OCP) indicating faster orientational relaxation. The possible origins for the observed trends in the reorientation time constant are discussed.

The main purpose of this work is study of electrochemical hydrogen peroxide and ascorbate reactions on electrodes modified by Prussian blue (PB), with the aim to apply these electrodes in creation of sensors and biosensors. For this purpose, a detailed study of electrochemical reduction of hydrogen peroxide, as well as of oxidation of ascorbate at Prussian blue modified rotating disk electrode. In view of the results obtained, a mechanism for hydrogen peroxide reduction at PB modified electrode has been proposed. In accordance with this mechanism, electron transfer appears to be rate-limiting step. The kinetics of decomposition of PB modified electrode in the course of a cathodic reduction of hydrogen peroxide has been studied, and the influence of different factors to this process has been determined. Prototypes of sensors and biosensors, for different analytes have been elaborated and tested.
Darbo tikslas yra elektrocheminių vandenilio peroksido ir askorbato reakcijų tyrimas ant Berlyno mėlynuoju (BM) modifikuotų elektrodų, siekiant pritaikyti šiuos elektrodus jutiklių ir biojutiklių kūrimui. Ištirta vandenilio peroksido redukciją ir askorbato oksidaciją naudojant sukamojo disko elektrodą. Gauti rezultatai galimai įrodo stadijinį vandenilio peroksido katodinės redukcijos mechanizmą vykstantį ant BM modifikuoto elektrodo. Detaliai ištirta BM sluoksnio irimo kinetika vandenilio peroksido elektroredukcijos metu, ir nustatyti faktoriai, įtakojantys irimo proceso greitį. Sukurti jutiklių ir biojutiklių prototipai, kurie galėtų būti panaudoti biologiškai aktyvių medžiagų (vandenilio peroksido, askorbato, gliukozės) nustatymui.

Danas, u raznim analitičkim laboratorijama postoji veći broj analitičkih protokola,zasnovanih bilo na izuzetno sofisticiranim ili jednostavnijim tehnikama, koji služe zaodređivanje različitih ciljnih analita od farmakološkog značaja. Među tim grupama ciljnih analita pripadaju i antibiotici koji predstavljaju veliko otkriće u oblasti medicine i zahvaljujući njima spašeno je više od sedam miliona života, ali pored navedenih koristi, antibiotici mogu da izazovu  veliki broj neželjenih efekata i žučne kiseline zajedno sa svojim derivatima, koji su fiziološki deterdženti, mogu biti citotoksične za organizam ako se njihova koncentracija ne kontroliše. U ovoj doktorskoj disertaciji prikazan je razvoj analitičkih metoda pre svega voltametrijskihmetoda u kombinaciji sa jednostavnim i savremenim elektrodama/senzorima za određivanje  odabranih analita kao što je antraciklični antibiotik doksorubicin (DOX), makrolidni antibioticieritromicin-etilsukcinata (EES), azitromicina (AZI), klaritromicina (CLA) i roksitromicina  (ROX) i 3-dehidro-deoksiholne kiseline.Voltametrijska karakterizacija i određivanje gore navedenih antibiotika primenom obnovljive srebro-amalgam film elektrode (Hg(Ag)FE)rađena je direktnom katodnom  voltametrijom sa pravougaonim talasima (SWV) i visoko osetljivom adsorptivnom voltametrijom sa pravougaonim talasima (SW-AdSV) u Briton-Robinson puferu, kao pomoćnom elektrolitu, obuhvatajući širok opseg pH vrednosti. Odgovor DOX-a primenom  Hg(Ag)FE praćen je u intervalu potencijala od -0,20 do -0,80 V.  Za analizu tragova, optimizacija metode ukazuje da su optimalni parametri za analitički pik na potencijalu (Ep ) -0,57 V u odnosu na zasićenu kalomelovu elektrodu (ZKE): pH 6,0, potencijal  akumulacije -0,20 V i vreme  akumulacije 140 s. U model rastvoru, DOX je određivan u koncentracionom opsegu 4,99-59,64  ng mL^-1. Razvijena SW-AdSV metoda je primenjena za određivanje DOX-a u obogaćenom uzorku humanog urina. Niža koncentracija DOX-a 9,89ng mL^-1 u voltametrijskoj  ćeliji je određivana sa relativnom standardnom devijacijom (RSD) manjom od 6,0%. Što se ispitivanih makrolida tiče oni su pokazali redukcione signale u dalekoj negativnoj oblasti potencijala. Ispitivanja direktnom katodnom SWV rađena su u opsegu potencijala od -0,75 V do -2,00 V u odnosu na ZKE, pri čemu su dobijena jedan ili dva redukciona pika u opsegu potencijala od -1,5 V do -1,9 V. Oblik i intenzitet signala zavisi od primenjene pH vrednosti u širokoj pH oblasti. Za analitičke svrhe, radi razvoja direktne katodne SWV i adsorptivne inverzne/striping SWV metode, pogodnim su se pokazale neutralna i slabo alkalna sredina tj. pH 7,0 sa  E_p na -1,67 V u odnosu na ZKE za ROX i EES i pH 7,2 sa E_p na -1,85 V u odnosu na ZKE za AZI i pH 7,4 sa E_p na -1,64 V u odnosu na ZKE za CLA. Na osnovu snimljenih cikličnih voltamograma na  optimalnim pH vrednostima, može se predložiti adsorptivno-kontrolisan kinetički proces na elektrodi u slučaju sva  četiri ispitivana jedinjenja. Takođe,  ¹H NMR merenja uz potiskivanje  signala vode u pH oblasti između pH 6,0 i 10,5 ukazuju na to da su makrolidni molekuli pri optimalnim analitičkim uslovima predominantno u protonovanoj formi preko tercijerne amino grupe što potpomaže, u sva  četiri slučaja, njihovu adsorpciju na odgovarajuće polarizovanoj Hg(Ag)FE. Optimizovane direktne katodne SWV metode  pokazuju dobru linearnost u koncentracionom opsegu 4,81-23,3  µg mL^-1 , 4,53-29,8  µg mL^-1 , 1,96-28,6  µg mL^-1 i 1,48-25,9 µg mL^-1 za AZI, EES, CLA odnosno ROX. Razvijene SW-AdSV metode rezultiraju u linearnom odgovoru pri nižim koncentracionim intervalima 1,0-2,46 µg mL^-1 ,  0,69-2,44  µg mL^-1, 0,05-0,99 µg mL^-1 i 0,10-0,99  µg mL^-1 , za AZI, EES, CLA i ROX. RSD za sve razvijene metode nije veća od 1,5% izuzev SWV metode u slučaju AZI-a gde je 4,5%. Direktna katodna SWV metoda  je uspešno primenjena za određivanje EES-a u farmaceutskom proizvodu Eritromicin^® dok SW-AdSV metoda je primenjena u slučaju određivanja EES-a u obogaćenom uzorku humanog urina i za određivanje ROX-a u farmaceutskom proizvodu Runac^® . U svim pomenutim slučajevima, primenjena je metoda standardnog dodatka. Pouzdanost i tačnost elaboriranih procedura u slučaju određivanja EES-a u model sistemu i  farmaceutskom proizvodu Eritromicin^® su potvrđena poređenjem sa rezultatima dobijenim primenom HPLC-DAD metode.Nakon preliminarnih studija 3-dehidro-deoksiholne  kiseline/3-dehidro-deoksiholata primenom elektrode od staklastog ugljenika (GCE), gde je uočeno da ne dolazi do formiranja redukcionog signala u Briton-Robinson puferu između pH 5,0 i 11,8 primenom direktne katodne SWV, bizmut-film je izdvojen  ex situ na površini iste elektrode od staklastog ugljenika (BiF-GCE) iz uobičajeno korišćenog rastvora za elektrodepoziciju (0,02 mol L^-1 Bi(NO₃)₃, 1,0 mol L^-1 HCl i 0,5 mol L^-1 KBr) i tako pripremljena elektroda je primenjena za karakterizaciju i određivanje pomenutog jedinjenja u alkalnoj sredini. Redukcioni signal ispitivanog analita od analitičkog značaja je uočen jedino primenom BiF-GCE u Briton-Robinson puferusa pH vrednostima između 9,5 i 11,8 u režimu adsorptivne inverzne/stripingvoltametrije sa pravougaonim talasima, dok u slučaju direktnih katodnih SWV eksperimentalnih uslova uočen je slab redukcioni pik sa niskom strujom maksimuma pika. Optimizovani eksperimentalni uslovi za određivanje 3-dehidro-deoksiholata obuhvataju odgovarajuće kondicioniranje elektrode uključujući kondicioniranje  ex situ pripremljene BiF-GCE u Briton-Robinson pomoćnom elektrolitu pH 11,8 do stabilizacije struje bazne linije elektrohemijskim cikliranjem potencijala radne elektrode u potencijalskom opsegu između -1,00 i -2,00 V u odnosu na ZKE (blizu 15 puta) i primenu dva ključna parametara adsorptivne voltametrije sa pravougaonim talasima: vreme akumulacije od 30 s i potencijal akumulacije  -1,00 V u odnosu na ZKE. Zbog relativne asimetričnosti dobijenih redukcionih signala ispitivanog analita sa  E_p na -1,35 V u odnosu na ZKE, što je takođe prisutno i u slučaju primene SW-AdSV, određivanje ispitivanog analita je zasnovano na linearnoj zavisnosti između površine pika redukcionog signala  spitivanog analita i njegove odgovarajuće koncentracije i postignuta granica detekcije je 1,43 µg mL^-1 sa dva linearna opsega kalibracione krive od 4,76 µg mL^-1 do 13,0 µg mL^-1 i od 13,0 µg mL^-1 do 23,1 µg mL^-1 za razvoj analitičke metode. RSD metode je 3,22%. Dodatni eksperimenti, elektroliza ispitivanog analita na potencijalu -1,55 V (blizu maksimuma pika ciljnog analita) u odnosu na ZKE su rađeni primenom GCE u obliku ploče (površina 33,52 cm 2 ) modifikovane sa  ex situ pripremljenim bizmut-filmom. Rastvor od interesa uzorkovan je na početku eksperimenta, nakon 2,5 h i nakon 4,5 h tretmana. Ovakvi uzorci su analizirani primenom ¹H NMR merenja uz potiskivanje signala vode u puferskom rastvoru pH 11,8. Može se pretpostaviti da tokom elektrolize 3-dehidro-deoksiholata dolazi do redukcije keto grupe prisutne u strukturi ispitivanog analita.Na osnovu literaturnih podataka da neki od ciljnihmakrolidnih antibiotika kao što je npr. azitromicin pokazuju oksidativno ponašanje na elektrodi od ugljenične paste i elektrodi od zlata deteljna karakterizacija i određivanje  četiri makrolidna antibiotika rađena je primenom  asične elektrode od ugljenične paste (CPE) koja se sastoji samo od grafitnog praha i parafinskog ulja sa optimizovanih direktnih anodnih SWV metoda. U slučaju EES-a i AZI-a diferencijalna pulsna voltametrija (DPV) je testirana za iste svrhe. Ključni  parametar u slučaju razvoja analitičkih voltametrijskih metoda je odabir pH vrednosti pomoćnog elektrolita gde je oblik/simetričnost i intenzitet oskidacionog pika glavni kriterijum prilikom odabira. Kao odgovarajuće pH vrednosti za voltametrijsko određivanje EES-a primenom SWV metode odabrana je pH 8,0 sa E_p na 0,83V u odnosu na ZKE, dok u slučaju DPV metode pH 12,0 sa  E_p na 0,55 V u odnosu na ZKE je bila najpogodnija za analitičke svrhe. Za određivanje AZI-a, u slučaju obe SWV i DPV metode pH 7,0 se pokazala najpogodnijom sa E_p analitičkog signala na 0,85 V odnosno 0,80 V u odnosu na ZKE, dok u slučaju CLA i ROX koji su ispitivani samo primenom SWV metode za analitičke svrhe pH 12,0 je bila najpogodnija sredina sa E_p analitičkog signala na 0,65 V odnosno na 0,63 V u odnosu na ZKE. Postignute granice detkcije primenom nemodifikovane CPE i direktne anodne SWV su uglavnom u submikrogramskom koncentracionom opsegu 0,17 µg mL^-1 , 0,32  µg mL^-1 i 0,30  µg mL^-1, u slučaju EES-a, AZI-a i ROX-a i u niskom mikrogramskom koncentracionom opsegu 1,43  µg mL^-1 za CLA. Razvijena SWV metoda sa jednostavnom CPE pokazala se pogodnom za određivanje ROX-a u komercijalnom proizvodu Runac^® tableti. U slučaju optimizovanih DPV metoda postignute granice detekcije za EES i AZI su u niskom mikrogramskom  koncentracionom opsegu 1,03  µg mL^-1 odnosno 1,53  µg  mL^-1 . U želji da se postigne niža granica detekcije za AZI, DPV metoda  je testirana u kombinaciji sa  CPE radnom elektrodom površinski modifikovanom sa zlatnim nanočesticama  prečnika 10 nm (Au-CPE) i  postignuta granica detekcije je 0,95  µg mL^-1 sa  E_p analitičkog signala na 0,80 V u odnosu na  ZKE. RSD metode u slučaju Au-CPE je 3,5%, dok je u slučaju nemodifikovane CPE 6,0%.  Linearnost analitičke metode zasnovane na primeni Au-CPE je dva puta šira nego u slučaju  primene nemodifikovane CPE.Na osnovu dobijenih rezultata može se zaključiti da  odgovarajuće kombinacije  optimizovanih voltametrijskih tehnika sa ekološki prihvatljivim i lako primenljivim radnim  elektrodama, kao što su Hg(Ag)FE, BiF-GCE i CPE zajedno sa Au-CPE, rezultuju razvojem  pouzdanih analitičkih metoda, kako u oksidacionim tako i u redukcionim proučavanjima, koje  često omogućuju  određivanje tragova analita od farmakološkog značaja u jednostavnim, a u nekim slučajevima i u složenim sistemima. 
Nowadays in different analytical laboratories there is the increasing number of analytical protocols, either based on highly sophisticated or simpler measurements techniques, which serving for determination of different target analytes of pharmacological importance. Among such target groups of the analyte belongs the antibiotics which present a great discovery in the field of medicine and thanks to them were saved more than seven million people but beside to the mentioned great benefits, antibiotics can cause a large number of side effects and bile acids together with their derivatives which are physiological detergents but if their concentration is notcontrolled they can be cytotoxic to the body. In the present doctoral dissertation the development of analytical methods, primarily analytical voltammetric methods in combination with simple and contemporary electrodes/sensors, for the determination of selected analytes as antracycline antibiotic doxorubicin (DOX), macrolide antibiotics erythromycin ethylsuccinate (EES), azithromycin (AZI), clarithromycin (CLA) and roxithromycin (ROX) and 3-dehydrodeoxycholic acid were performed.Voltammetric characterization and determination of the above mentioned antibiotics using a renewable silver-amalgam film electrode (Hg(Ag)FE) was performed by direct cathodic square-wave voltammetry (SWV) and by highly sensitive adsorptive square-wave voltammetry (SW-AdSV) in aqueous Britton-Robinson buffer solutions as supporting electrolyte covering the wider pH range. The Hg(Ag)FE response of DOX was monitored in the potential range between -0.20 and -0.80 V. For the trace level analysis the method optimization showed that the optimal conditions for the analytical peak with peak potential (E_p) at -0.57 V vs. SCE were: the pH 6.0, the accumulation potential -0.20 V, and the accumulation time 140 s. In the model solutions, DOX was determined in the concentration range of 4.99-59.64 ng mL^-1. The developed SWAdSV method was applied for the determination of DOX in spiked human urine sample. The lowest concentration of DOX of 9.89 ng mL^-1 in voltammetric vessel was determined with the relative standard deviation (RSD) less than 6%. As for the investigated macrolides, they showed reduction signals in fairly negative potential range. During direct cathodic SWV investigations conducted over the potential range from -0.75 V to -2.00 V vs. SCE, either one or two reduction peaks were obtained in the  potential range from -1.5 to -1.9 V. For analytical purposes concerning the development of direct cathodic SWV and adsorptive stripping SWV methods the neutral  and slightly alkaline media were suitable as pH 7.0 with E_p at -1.67 V vs.  SCE for ROX and EES and pH 7.2 and pH 7.4 with E_p at -1.85 V and -1.64 V vs. SCE for AZI and CLA, respectively. Based on the cyclic voltammograms recorded at these pH values, adsorptioncontrolled electrode kinetics process can be proposed for all four investigated compounds. The water suppressed ¹H NMR measurements in the pH range between 6.0 and 10.5 indicated that the macrolide molecules at the optimal analytical conditions are predominantly in protonated form via their tertiary amino groups which supported in all four cases their adsorption on the appropriately polarized Hg(Ag)FE electrode. The optimized direct cathodic SWV methods showed good linearity in concentration ranges 4.81-23.3 μg mL^-1, 4.53-29.8 μg mL^-1, 1.96-28.6  μg mL^-1, and 1.48-25.9 μg mL^-1 for AZI, EES, CLA and ROX, respectively. The SW-AdSV methods resulted in the linear responses at lower concentration ranges as 1.0-2.46 μg mL^-1, 0.69- 2.44 μg mL^-1, 0.05-0.99 μg mL^-1 and 0.10-0.99 μg mL^-1, for AZI, EES, CLA and ROX, respectively. The RSD for all developed methods was not higher than 1.5% except the SWV method for AZI with 4.7%. The direct cathodic SWV method was successfully applied for the determination of EES in the pharmaceutical preparation Eritromicin^®, while SW-AdSV was tested in the case of the spiked urine sample and for determination of ROX in pharmaceutical preparation Runac^®. In all above cases, the standard addition method was used. The reliability and accuracy of the above procedures in the case of EES determination in model system and pharmaceutical preparation Eritromicin^® were validated by comparing them with those obtained by means of HPLC-DAD measurements.After initial study of 3-dehydro-deoxycholic acid/3-dehydro-deoxycholate by glassy carbon electrode, where the absence of any reduction peak was observed in the Britton-Robinson buffer solutions between pH 5.0 and 11.8 by direct cathodic SWV, a bismuth-film was electrodeposited ex situ on the same glassy carbon electrode surface (BiF-GCE) from the usually used plating solution (0.02 mol L^-1 Bi(NO₃)₃, 1.0 mol L^-1 HCl and 0.5 mol L^-1 KBr) and such prepared film-electrode was applied for the characterization and determination of the the target analyte in alkaline media. The reduction signal of analytical importance was observed only by BiF-GCE in Britton-Robinson buffer solutions with pH values between 9.5 and 11.8 in adsorptive stripping square-wave voltammetry working regime, while in the case of the direct cathodic SWV experimental protocol only a very poor reduction peak was obtained. The optimized experimental conditions for the 3-dehydro-deoxycholate determination consist of the optimized electrode conditioning including the electrochemical cycling of the ex situ prepared BiF-GCE potentials in the potential span between -1.0 and -2.0 V vs. SCE (nearly 15 times) in the Britton-Robinson supporting electrolyte pH 11.8 till the stabilization of the baseline current, and the application of two key parameters of the adsorptive square-wave voltammetric protocol: the accumulation time as 30 s and accumulation potential as -1.0 V vs. SCE. Because of the relative asymmetry of the obtained reduction signals of the target analyte with peak E_p at -1.35 V vs. SCE, which is still present in the case of the SW-AdSV, the quantification of the target analyte was based on the linear correlation between peak area of the reduction signal and its appropriate concentrations, and reached limit of detection is 1.43 μg mL^-1 and with two linear ranges of calibration curve from 4,76 μg mL^-1 to 13.0 μg mL^-1 and from 13,0 μg mL^-1 to 23,1 μg mL^-1 for the development of analytical method. The RSD of the method  was 3.22%. Additional experiments were performed applying GCE with rectangular form (area 35.32 cm²) modified with ex situ prepared bismuth-film for the electrolysis of the target analyte which was performed at the potential -1.55 V (nearly the peak maxima of the target analyte) vs. SCE. The solution of interest was sampled at the beginning of the experiment, after 2.5 h and after 4.5 h of treatment. Such samples were analysed by simply water suppressing ¹H NMR measurements in the buffered solution at pH 11.8. It can be assumed that during electrolysis of 3-dehydrodeoxycholate the reduction of the keto group present in the structure of the target analyte can be occurred.Driven by earlier literature data about the fact that some of the target macrolide antibiotics as e.g. azithromycin showed oxidation behavior at a carbon paste and gold working electrodes detailed characterization and determination of four target macrolide antibiotics were performed on classical carbon paste electrode (CPE) constituted only from graphite powder and paraffin oil with optimized direct anodic SWV methods. In the cases of EES and AZI differential pulse voltammetric (DPV) methods were tested for the same purpose as well. The key parameter in the case of the development of the analytical voltammetric methods is the selection of the pH value of the supporting electrolyte where the shape/simmetry and intensity of the oxidation peak were the criteria. As the appropriate pH value for determination of EES by SWV method the pH 8.0 was selected with E_p at 0.83 V vs. SCE while in the case of the DPV method the pH 12.0 with E_p at 0.55 V vs. SCE was the most suitable for analytical  purpose. As for AZI determination, in the case of both SWV and DPV methods the pH 7.0 was the most appropriate supporting electrolyte with the Ep of analytical signal at 0.85 V and 0.80 V vs. SCE, respectively, while in the case of CLA and ROX which were investigated only with SWV method for the analytical purposes the pH 12.0 was the most suitable with E_p at 0.65 V and at 0.63 V vs. SCE. The obtained detection limits applying the bare CPE and the direct anodic SWV are mainly  in submicrogram concentration range as 0.17 μg mL^-1; 0.32 μg mL^-1 and 0.30 μg mL^-1 for EES, AZI, and ROX and in the low microgram concentration range as 1.43 μg mL^-1 for the CLA, respectively. The developed method succesfully tested for the determination of ROX in the commercial formulation, Runac^® tablet. In the case of the optimized DPV methods the obtained detection limits for EES and AZI are in the low microgram concentration range 1.03 μg mL^-1 and 1.53 μg mL^-1, respectively. For the improvement of the sensitivity for AZI the DPV method was tested in combination with a  CPE working electrode surface modified with gold nanoparticles with diameter of 10 nm (Au-CPE) and reached the limit of detection was 0.95 μg mL^-1 at E_p of 0.80 V vs. SCE. The RSD of the method in the case of the Au-CPE is 3.5% while in the case of the native CPE 6.0%. The linearity of the Au-CPE based analytical method is twice wider then it is case with the bare CPE applying protocol.Based on the obtained results it can be conclude that the appropriate combination of the optimized voltammetric pulse techniques and the environmentally friendly and easy to use working electrodes as Hg(Ag)FE, BiF-GCE and CPE together with Au-CPE resulted in the development of reliable analytical method either in the oxidation or reduction studies, often allowing trace level determination of pharmacological importance target analytes in simpler and in some case complexes systems.

This thesis describes the development of new adsorptive cathodic stripping voltammetric methods for reliable determination of some trace metals in biological and environmental materials on a glassy carbon mercury film electrode. In particular, the development of these methods involved selection of a suitable complexing agent for the respective metal ion studied, characterization of the electrode processes, investigation of factors affecting the voltammetric response such as concentration and pH of supporting electrolyte, concentration of complexing agent, accumulation potential, accumulation time and electrode rotation rate. Also, organic and inorganic interferences, linear concentration range, and detection limits were carefully considered. Furthermore, the analytical application of the method was demonstrated for each metal in biological and/or environmental materials, after optimization of the sample decomposition procedure. Some conclusions : the results obtained by the AdCSV method for the determination of tin in juices agreed reasonably with those obtained by atomic absorption method; the use of the adsorptive voltammetric technique after dry-ashing and UV treatment of the samples was successfully demonstrated for the determination of vanadium in standard reference materials such as urban particulate matter, peach leaves, apple leaves and bovine liver; and, the use of the adsorptive stripping voltammetric technique, after decomposition of samples by dry-ashing and UV treatment, was successfully demonstrated for the determination of molybdenum in peach leaves, apple leaves and bovine liver samples.
Doctor of Philosophy (PhD)

This thesis concerns the development and the study of Iron-based water oxidation catalysts (WOCs) and how to immobilize them onto the hydrophobic surface of a carbon paste electrode. In the introductory chapter a general background of the field of water splitting and this thesis is given. In the second chapter, experimental performance is described from synthesis to measurements of a complete complex-doped electrode. The third chapter deals with the results and the discussion of the performed experiments. In chapter four, a descriptive conclusion of the obtained data is held.
Det här arbetet berör studien och utvecklingen utav järnbaserade katalysatorer, speciellt framtagna för för delning utav vatten. Utöver detta undersöks även om dessa katalysatorer (WOCs) kan immobiliseras på den hydrofoba ytan hos elektroder gjorda på kol-pasta. I det inledande kapitlet ges en generell bakgrund till området som berör delning utav vatten. I det andra kapitlet presenteras det experimentella utförandet utav synteser samt elektrokemiska mätningar som berörts under arbetets gång i jakten på en komplexdopad elektrod. I det tredje kapitlet diskuteras resultaten från mätningarna samt möjliga framtidsutsikter. I det fjärde kapitlet presenteras slutsatserna utav studien.

Prussian blue (PB) nanoparticles were synthesized from FeCl3.6H2O, K4[Fe(CN)6].3H2O, and from Fe(NO3)3.9H2O and K4[Fe(CN)6].3H2O, and then characterized by Fourier transform infrared (FT-IR), Ultraviolet-visible spectroscopy, X-ray diffraction (XRD), Energy dispersive spectroscopy (EDS), Scanning electron microscopy (SEM), Raman spectroscopy and thermogravimetric analysis. Graphene oxide and carbon nanotubes were also synthesized and characterized. PB nanoparticles, carbon nanotubes (CNT), graphene oxide (GO) and cetyltrimethylammonium bromide (CTAB) were sequentially deposited onto glassy carbon electrode surface to form chemically modified electrode for the detection of hydrogen peroxide (H2O2) and dopamine. The following electrodes were fabricated, GC-PB, GC-MWCNT, GCGO, GC-CTAB, GC-MWCNT-PB, GC-GO-PB and GC-CTAB-PB. Cyclic and Square wave voltammetric techniques were used to measure the hydrogen peroxide detectability of the electrodes at pH ranges of (3 - 7.4) in 0.1M phosphate buffer solution, in the absence or presence of 25 μL of H2O2. The GC-CNT-PB, GC-GO-PB,GC-CTAB-PB electrodes showed a good response for the detection of hydrogen peroxide in both acidic and neutral media while the GCPB electrode only showed good response in acidic media.

>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.