O manejo de fitoviroses muitas vezes é realizado com o uso de inseticidas para o controle do vetor. Para o patossistema Frankliniella zucchini / Cucurbita pepo / Zucchini lethal chorosis virus (ZLCV) não existe informação na literatura sobre a eficiência do controle da doença por meio do controle químico do vetor. Para tanto foi proposto este trabalho, que tem ainda por objetivo uma melhor compreensão da epidemiologia da doença em seus aspectos temporal e espacial. Os experimentos foram conduzidos na estação experimental de Fitopatologia da Escola Superior de Agricultura \"Luiz de Queiroz\" no período de março de 2010 a dezembro de 2011. Campos de abobrinha de moita foram divididos em parcelas com e sem aplicação do inseticida neonicotinóide Imidacloprid. As avaliações da doença foram feitas com base nos sintomas foliares característicos da doença, em intervalos de três a quatro dias, e confirmados por meio de teste ELISA. A Clorose Letal apresentou incidências de 11,58% e 52,55% em parcelas com inseticida e de 21,36% e 69,89% em parcelas sem inseticida, para os anos de 2010 e 2011, respectivamente. Em todos os casos, o modelo monomolecular apresentou melhor ajuste aos dados temporais e as plantas sintomáticas distribuíram-se aleatoriamente nas parcelas. Esses resultados sugerem que a disseminação primária é o processo predominante na epidemiologia da doença. A disseminação primária, neste caso, dá-se pelo influxo de vetores virulíferos de fora para dentro da plantação. O pequeno efeito benéfico do uso de inseticida está ligado ao controle da disseminação secundária da doença, de planta infectada para planta sadia dentro da plantação. Para o manejo racional da Clorose Letal é importante a determinação de hospedeiros alternativos do vírus e sua importância epidemiológica. O uso de inseticida, feito isoladamente, não é uma maneira eficiente de controlar da doença. / Management of virus diseases is often accomplished with insecticide spray to vector control. For pathosystem Frankliniella zucchini / Cucurbita pepo / Zucchini lethal chlorosis virus (ZLCV) there are no information about the efficiency of disease control by mean of vector chemical control. This research was proposed to fill this gap and, additionally, to better understand the epidemiology of the disease in its temporal and spatial aspects. Experiments were conducted at the experimental station of the Plant Pathology Department of ESA Luiz de Queiroz from March 2010 to December 2011. Fields of zucchini plants were divided into parcels, with and without insecticide application (Imidacloprid). Disease assessments were made based on disease symptoms at intervals of three to four days and confirmed by ELISA test. Lethal Chlorosis presented incidences of 11.58% and 52.55% in parcels with insecticide and of 21.36% and 69.89% in parcels without insecticide, for years 2010 and 2011, respectively. In all cases, the monomolecular model fitted better temporal data and symptomatic plants were distributed at random. These results suggest that primary dissemination is the predominant process in the epidemiology of the disease. Primary dissemination, in this case, is represented by the influx of viruliferous vectors from outside the field. The small effect caused by the use of insecticide is linked to the control of secondary dissemination inside the field. To manage rationally Letal Chlorosis it is important to identify the alternative hosts of virus and to determine its epidemiological relevance. Only to spray insecticide is not an efficient way for disease control in this case.

O manejo de fitoviroses muitas vezes é realizado com o uso de inseticidas para o controle do vetor. Para o patossistema Frankliniella zucchini / Cucurbita pepo / Zucchini lethal chorosis virus (ZLCV) não existe informação na literatura sobre a eficiência do controle da doença por meio do controle químico do vetor. Para tanto foi proposto este trabalho, que tem ainda por objetivo uma melhor compreensão da epidemiologia da doença em seus aspectos temporal e espacial. Os experimentos foram conduzidos na estação experimental de Fitopatologia da Escola Superior de Agricultura \"Luiz de Queiroz\" no período de março de 2010 a dezembro de 2011. Campos de abobrinha de moita foram divididos em parcelas com e sem aplicação do inseticida neonicotinóide Imidacloprid. As avaliações da doença foram feitas com base nos sintomas foliares característicos da doença, em intervalos de três a quatro dias, e confirmados por meio de teste ELISA. A Clorose Letal apresentou incidências de 11,58% e 52,55% em parcelas com inseticida e de 21,36% e 69,89% em parcelas sem inseticida, para os anos de 2010 e 2011, respectivamente. Em todos os casos, o modelo monomolecular apresentou melhor ajuste aos dados temporais e as plantas sintomáticas distribuíram-se aleatoriamente nas parcelas. Esses resultados sugerem que a disseminação primária é o processo predominante na epidemiologia da doença. A disseminação primária, neste caso, dá-se pelo influxo de vetores virulíferos de fora para dentro da plantação. O pequeno efeito benéfico do uso de inseticida está ligado ao controle da disseminação secundária da doença, de planta infectada para planta sadia dentro da plantação. Para o manejo racional da Clorose Letal é importante a determinação de hospedeiros alternativos do vírus e sua importância epidemiológica. O uso de inseticida, feito isoladamente, não é uma maneira eficiente de controlar da doença. / Management of virus diseases is often accomplished with insecticide spray to vector control. For pathosystem Frankliniella zucchini / Cucurbita pepo / Zucchini lethal chlorosis virus (ZLCV) there are no information about the efficiency of disease control by mean of vector chemical control. This research was proposed to fill this gap and, additionally, to better understand the epidemiology of the disease in its temporal and spatial aspects. Experiments were conducted at the experimental station of the Plant Pathology Department of ESA Luiz de Queiroz from March 2010 to December 2011. Fields of zucchini plants were divided into parcels, with and without insecticide application (Imidacloprid). Disease assessments were made based on disease symptoms at intervals of three to four days and confirmed by ELISA test. Lethal Chlorosis presented incidences of 11.58% and 52.55% in parcels with insecticide and of 21.36% and 69.89% in parcels without insecticide, for years 2010 and 2011, respectively. In all cases, the monomolecular model fitted better temporal data and symptomatic plants were distributed at random. These results suggest that primary dissemination is the predominant process in the epidemiology of the disease. Primary dissemination, in this case, is represented by the influx of viruliferous vectors from outside the field. The small effect caused by the use of insecticide is linked to the control of secondary dissemination inside the field. To manage rationally Letal Chlorosis it is important to identify the alternative hosts of virus and to determine its epidemiological relevance. Only to spray insecticide is not an efficient way for disease control in this case.

Résumé trop long / Mosquitoes transmit several human and animal diseases and their control represents a public health challenge worldwide. In most tropical countries, efficient control of mosquitoes relies on the use of chemical insecticides targeting adults or larvae. However, resistance to the four main classes of chemical insecticides has been reported worldwide and threatens vector control programs. In this context, there is an urgent need to find alternatives to conventional insecticides used in vector control. In this thesis, I explored the potential use of the neonicotinoid insecticide imidacloprid for mosquito control, focusing on the identification of metabolic resistance mechanisms, cross-resistance with other insecticides and the impact of environmental pollutants on imidacloprid tolerance. The mosquito Aedes aegypti was used as a model species for this research work. Basal tolerance of Ae. aegypti to imidacloprid was first evaluated at the larval and adult stages. Effects of a larval exposure across a single generation to a sub-lethal dose of imidacloprid were then investigated at the toxicological and molecular levels using transcriptome profiling. Short sub-lethal exposures were also used to identify potential cross-responses between imidacloprid, other chemical insecticides and anthropogenic pollutants. Long-term adaptive response of Ae. aegypti to imidacloprid was then investigated across several generations by selecting an insecticide-susceptible strain (Bora-Bora strain) with imidacloprid at the larval stage for 14 generations in the laboratory. Such artificial selection allowed obtaining the Imida-R strain. This strain showed an increased resistance to imidacloprid in larvae while no significant resistance was measured in adults. Resistance mechanisms were then investigated using various approaches including the use of detoxification enzyme inhibitors, biochemical assays and transcriptome profiling with DNA microarray and massive mRNA sequencing. Several protein families potentially involved in resistance were identified including detoxifications enzymes and cuticle proteins. Among the formers, 8 cytochrome P450s and 1 glutathione S-transferase appears as good candidates for a role in imidacloprid metabolism. The role of P450s in the elevated resistance of the Imida-R strain was confirmed by comparative P450-dependent in vitro metabolism assays conducted on microsomal fractions of the susceptible and Imida-R strains. At the gene level, substrate binding modeling allowed restricting the panel of P450 candidates. Meantime, heterologous expression of one P450 was performed and its ability to metabolize imidacloprid confirmed. Bioassay with other insecticides revealed potential cross-resistance of the Imida-R at the larval stage to other neonicotinoids but also to an insect growth inhibitor and in a lesser extent to DDT, confirming the probable role of detoxification enzymes. Relaxing the selection pressure of the Imida-R strain for few generations led to a rapid decrease of resistance, suggesting a cost of resistance mechanisms. Comparing the inducibility of candidate detoxification genes by imidacloprid in susceptible and resistant strains revealed a higher induction of these genes in the resistant strain, suggesting the selection of both a higher constitutive expression but also a greater phenotypic plasticity of these enzymes in the Imida-R strain. Finally, the potential role of cuticle protein in resistance was preliminary investigated by exposing larvae to a chitin synthesis inhibitor before bioassays. Overall, although this research work requires additional functional validation experiments, these data provide a better understanding of imidacloprid resistance mechanisms in mosquitoes and its potential use as an alternative to conventional insecticides in vector control.

Soil fauna provides processes of crucial importance for ecosystem functions, but our ability to observe their actions often depend on destructive methods where the integrity of the studied environment (the soil) is compromised. In this study, I develop and test a new generation of environmental monitoring tools that utilize vibrations made by soil macrofauna to inform about their performance and health. Three hypotheses were tested on forest ants (Formica sp.): (i) vibrations on a naturally occurring substrate can be used to measure the activity of ants, (ii) the vibrational signature of ants can inform us about the ants’ health, and (iii) behavior (locomotory activity, foraging etc.) of ants is correlated to specific vibrational signal characteristics. Vibrational signals from ant sub-populations (5 individuals/sample) were recorded on natural substrates (leaves) before and after exposure to sub-lethal levels of a contaminant with known negative effects on ants (imidacloprid). Activity was successfully detected from the inferred vibration oscillograms. However, neither the number of vibrational signals captured, or the signal characteristics changed after imidacloprid exposure, indicating that either the exposure was too low to generate a change in behavior or that the technique was unable to detect subtle changes in behavior. Signals of short duration and amplitude were generated by locomotory activity, but their intensity was dependent on the distance to the vibrometers laser focus point. Longer signal segments were either continuous, random, or rhythmic in their distribution. I suggest that these signals are a result of methodological artifacts, movement of multiple ants, and stridulation/drumming on the substrate, respectively. My findings suggest that this advanced monitoring tool is sensitive enough to capture activity from only a few ants, but the characteristics and number of captured signals are strongly affected by the measured substrate

No description available.

Bumblebees have undergone dramatic declines both in Britain and further afield during the last century. Bumblebees provide a crucial pollination service to both crops and wild flowers. For these reasons, they have received a great deal of research attention over the years. However, the ecology of wild bumblebee nests and the interactions between nests and other species, particularly vertebrates has been somewhat understudied. This is largely due to the difficulty in finding sufficient nests for well replicated study and a lack of appropriate methods of observation. Here, methods for locating bumblebee nests were trialled. It was found that a specially trained bumblebee nest detection dog did not discover nests any faster than people who had received minimal instruction. Numbers of nest site searching queens provide a reliable indication of suitable nesting habitat (i.e. places where nests are more likely to be found). In order to investigate aspects of bumblebee nesting ecology wild nests were observed by filming or regular observations by either researchers or members of the public. Some buff-tailed bumblebee (Bombus terrestris) nests were collected and all the bumblebees were genotyped to identify any foreign individuals. A review of British mammalian dietary literature was conducted to identify those that predate bumblebees. Great tits (Parus major) were filmed predating bumblebees at nests and it was clear from the literature and observations that badger (Meles meles), pine martens (Martes martes) and hedgehogs (Erinaceus europaeus) predate bumblebee nests, as well as the wax moth (Aphomia sociella). No evidence for predation by any other vertebrate species was found. Behaviours recorded included parasitism by Psithyrus, apparent nectar theft and possible usurpation by true bumblebees, egg-dumping by foreign queens and drifting and drifter reproduction by foreign workers. These events may cause harm to colonies (for example, through horizontal transmission of pathogens, or exploitation of the host nest’s resources). Alternatively where for example, usurpation by true bumblebees, egg-dumping or drifting is successful, these alternative reproductive strategies may increase the effective population size by enabling a single nest to produce reproductives of more than one breeding female. These data found that wild buff-tailed bumblebees (B. terrestris) nests with a greater proportion of workers infected with Crithidia bombi were less likely to produce gynes than those with fewer infected workers. Gyne production also varied dramatically between years. There is a growing body of evidence that a class of frequently used insecticides called neonicotinoids are negatively impacting bumblebees. An experiment was conducted using commercial colonies of buff-tailed bumblebees (B. terrestris) which were fed pollen and nectar which had been treated with the neonicotinoid imidacloprid at field realistic, sub-lethal levels. Treated colonies, produced 85-90% fewer gynes than control colonies. If this trend is representative of natural nests feeding on treated crops, for example, oilseed rape and field beans or garden flowers, then this would be expected to cause dramatic population declines. In this thesis methods for locating bumblebee nests have been tested, new behaviours have been identified (for example, egg-dumping by queens and predation by great tits) and estimations for rates of fecundity and destruction by various factors have been provided. Doubt has been cast over the status of some mammals as predators of bumblebee nests and estimates for gyne production, nest longevity, etc, have been given. More work is needed, especially observations of incipient nests as this is when the greatest losses are thought to occur.

<p><!--[if gte mso 9]><xml> <w:WordDocument> <w:View>Normal</w:View> <w:Zoom>0</w:Zoom> <w:PunctuationKerning /> <w:ValidateAgainstSchemas /> <w:SaveIfXMLInvalid>false</w:SaveIfXMLInvalid> <w:IgnoreMixedContent>false</w:IgnoreMixedContent> <w:AlwaysShowPlaceholderText>false</w:AlwaysShowPlaceholderText> <w:Compatibility> <w:BreakWrappedTables /> <w:SnapToGridInCell /> <w:WrapTextWithPunct /> <w:UseAsianBreakRules /> <w:DontGrowAutofit /> </w:Compatibility> <w:BrowserLevel>MicrosoftInternetExplorer4</w:BrowserLevel> </w:WordDocument> </xml><![endif]--><!--[if gte mso 9]><xml> <w:LatentStyles DefLockedState="false" LatentStyleCount="156"> </w:LatentStyles> </xml><![endif]--><!--[if gte mso 10]> <mce:style><! /* Style Definitions */ table.MsoNormalTable {mso-style-name:"Table Normal"; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-parent:""; mso-padding-alt:0pt 5.4pt 0pt 5.4pt; mso-para-margin:0pt; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:10.0pt; font-family:"Times New Roman"; mso-ansi-language:#0400; mso-fareast-language:#0400; mso-bidi-language:#0400;} --><!--[endif] --></p><p class="MsoBodyText" style="margin-bottom: 0.0001pt;">U disertaciji je izvr&scaron;ena voltametrijska karakterizacija i određivanje pet&nbsp;neonikotinoidnih insekticida (imidakloprida, tiametoksama, klotianidina, nitenpirama i&nbsp;acetamiprida) na različitim elektrodama na bazi ugljenika, kao &scaron;to su elektroda od&nbsp;ugljenične paste, elektroda od staklastog ugljenika i bizmut-filmom modifikovani&nbsp;staklasti ugljenik. Pored ispitivanja u model-rastvorima, razvijene visokoosetljive&nbsp;diferencijalne pulsne voltametrijskemetode su primenjene za određivanje neonikotinoida&nbsp;u realnim uzorcima. Neonikotinoidi su određivani u uzorcima rečne vode i komercijalnim&nbsp;formulacijama, a praćena je i njihova fotolitička i fotokatalitička razgradnja. Radi&nbsp;potvrđivanja voltametrijskih rezultata, izvedena su komparativna merenja uz primenu&nbsp;tečne hromatografije sa detektorom od niza dioda i infracrvenespektrometrije. Detekcija&nbsp;pojedinih degradacionih proizvoda nastalih u toku ispitivanih fotodegradacionih procesa&nbsp;je praćena tečnohromatografskom metodom sa tandemskom masenospektrometrijskom&nbsp;detekcijom. Proučavana je povr&scaron;inska struktura CR 5 grafitnog praha, elektrode od&nbsp;ugljenične paste na bazi trikrezil-fosfata i elektrode od staklastog ugljenika pomoću&nbsp;skenirajuće elektronske mikroskopije.</p> / <p>This thesis is concerned with the voltammetric characterization and&nbsp;determination of five neonicotinoid insecticides (imidacloprid, thiamethoxam,&nbsp;clothianidin, nitenpyram and acetamiprid) at different carbon-based electrodes such as&nbsp;carbon paste, glassy carbon and bismuth-film modified glassycarbon. In addition to the&nbsp;investigations in model solutions, the developed highly sensitive differential pulse&nbsp;voltammetric methods were applied for the determination of neonicotinoids in real&nbsp;samples. Neonicotinoids were determined in river water samples, commercial&nbsp;formulations, and their photolytic and photocatalytic degradation was also monitored. To&nbsp;confirm the voltammetric results, comparative measurements were performed by liquid&nbsp;chromatography with diode-array detector and infrared spectrometry. Detection of some&nbsp;degradation products formed during the photodegradation processes was monitored using&nbsp;liquid chromatography with tandem mass-spectrometric detection. The surface structure&nbsp;of CR 5 graphite powder, tricresyl phosphate-based carbon paste electrode and glassy&nbsp;carbon electrode was investigated by scanning electron microscopy.</p>

<p>U okviru ove doktorske disertacije, razvijene su elektroanalitičke metode za određivanje odabranih pesticida primenom hronopotenciometrije. Ispitana je mogućnost primene elektrode od staklastog ugljenika i tankoslojne živine elektrode kao radnih elektroda za određivanje insekticida imidakloprida i herbicida metamitrona i metribuzina. U cilju optimizacije uslova hronopotenciometrijske tehnike, za svaki ispitivani sistem (pesticid/radna elektroda) ispitan je uticaj najznačajnijih eksperimentalnih parametara na analitički signal pesticida, uključujući mehanizam generisanja analitičkog signala na radnoj elektrodi (oksidacija/redukcija), optimalnu metodu za uklanjanje rastvorenog kiseonika iz analiziranog rastvora, kao i vrstu, pH i koncentraciju pomoćnog elektrolita. Nakon toga definisan je optimalni opseg potencijala i struje redukcije. Pored toga, u okviru validacije metode za svaki ispitivani sistem, ispitan je i definisan opseg linearnosti, određena granica detekcije i granica kvantifikacije, ispitana preciznost, tačnost, robusnost i selektivnost metode. Dobijeni analitički signal za ispitivane pesticide bio je posledica ireverzibilne redukcije analita na radnoj elektrodi, a za svaki analit dobijen je jedan redukcioni pik. U slučaju određivanja metribuzina eksperimenti su pokazali da se analitički signal ne može detektovati na elektrodi od staklastog ugljenika uz kori&scaron;ćenje dostupne instrumentacije. Ispitivanja u model-rastvorima za svaki ispitivani sistem pokazala su dobre karakteristike u pogledu preciznosti, tačnosti, selektivnosti i robusnosti metode. Najveća osetljivost za sva tri pesticida postignuta je uz primenu tankoslojne živine elektrode, a vrednosti granice detekcije iznosile su 0,17 mg/l za imidakloprid, 0,07 mg/l za metamitron i 0,04 mg/l za metribuzin. Nakon optimizacije i validacije, razvijene hronopotenciometrijske metode primenjene su na komercijalne formulacije pesticida i uzorke vode. U cilju dodatne potvrde hronopotenciometrijskih rezultata na uzorcima vode izvedena su komparativna merenja uz primenu hromatografske LC-MS/MS analize.</p> / <p>Within this doctoral dissertation, electroanalytical methods for the determination of selected pesticides using chronopotentiometry are developed. The possibility of using glassy carbon electrode and thin film mercury electrode as a working electrode for determination of insecticide imidacloprid and herbicides metamitron and metribuzin is investigated. In order to optimize the conditions of the chronopotentiometric technique for each tested system (pesticide/working electrode), the influence of the most important experimental parameters on the analytical signal of the pesticides is investigated, including the generating mechanism of the analytical signal on the working electrode (oxidation/reduction), the optimal method for removal of dissolved oxygen from the analyzed solution, as well as type, pH, and concentration of the supporting electrolyte. Afterwards, the optimal range of potential and reduction current is defined. Additionally, within the validation of the method for each tested system, the linearity range is determined and defined, limit of detection and quantification are determined, and precision, accuracy, robustness and selectivity of the method are tested. The obtained analytical signal for the investigated pesticides is the result of irreversible reduction of the analyte on the working electrode, and for each analyte one reduction peak is obtained. In the case of metribuzin determination, the experiments have shown that by using the available instrumentation the analytical signal can not be detected on the glassy carbon electrode. Investigation in model solutions for each tested system shows good characteristics in terms of precision, accuracy, selectivity and robustness of the method. The highest sensitivity for all three pesticides was achieved by using thin film mercury electrode, and values of detection limit were 0.17 mg/l for imidacloprid, 0.07 mg/l for metamitron and 0.04 mg/l for metribuzin. After optimization and validation, the developed chronopotentiometric methods are applied to commercial pesticide formulations and water samples. In order to further confirm the chronopotentiometric results on the water samples, comparative measurements are performed using chromatographic LC-MS/MS analysis.</p>

<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>