Submitted by TIAGO GAZOLA (tiago-gazola@hotmail.com) on 2017-09-12T15:48:47Z No. of bitstreams: 1 Tiago Gazola com ficha.pdf: 1538645 bytes, checksum: 1858094f7f52707ec423af3ef92da438 (MD5) / Approved for entry into archive by Monique Sasaki (sayumi_sasaki@hotmail.com) on 2017-09-12T17:59:13Z (GMT) No. of bitstreams: 1 gazola_t_me_bot.pdf: 1538645 bytes, checksum: 1858094f7f52707ec423af3ef92da438 (MD5) / Made available in DSpace on 2017-09-12T17:59:13Z (GMT). No. of bitstreams: 1 gazola_t_me_bot.pdf: 1538645 bytes, checksum: 1858094f7f52707ec423af3ef92da438 (MD5) Previous issue date: 2017-07-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / As infestações com Digitaria insularis em áreas de culturas anuais e os casos de resistência ao herbicida glyphosate aumentaram nos últimos anos, e estes fatos contribuíram para tornar a espécie uma das mais importantes plantas daninhas do Brasil. Diante disso, foram desenvolvidos experimentos que tiveram como objetivo confirmar a resistência de biótipos de D. insularis perenizados e propagados vegetativamente resistentes ao glyphosate, bem como, compreender o perfil metabólico do herbicida nestas plantas, verificar se existe alteração no controle relativo em função dos métodos de propagação empregados e determinar o fator de resistência nas progênies obtidas por sementes autofecundadas. Foram realizados três experimentos em casa de vegetação no delineamento inteiramente casualizado, sendo os dois primeiros com oito biótipos de capim-amargoso considerados como suscetíveis e três com suspeita de resistência ao herbicida glyphosate. No primeiro experimento foi avaliado o controle das plantas aos 7, 14, 21 e 28 dias após a aplicação (DAA) do glyphosate. No segundo experimento, avaliou-se o controle nas mesmas épocas do primeiro e 72 horas após a aplicação do herbicida foi quantificado o acúmulo de ácido chiquímico e ácido quínico, deposição, absorção e translocação de glyphosate, concentração de AMPA, dos aminoácidos aromáticos (fenilalanina, tirosina e triptofano) e ácido salicílico. No terceiro experimento foram conduzidas curvas de dose-resposta com glyphosate nas doses de 0; 90; 180; 360; 720; 1440; 2880 e 5760 g e.a. ha-1, na progênie de quatro biótipos, e foram avaliados o controle e a massa seca aos 21 DAA para obtenção do fator de resistência. O método de propagação vegetativa se mostrou consistente e não alterou a resposta dos biótipos nos testes de fitointoxicação por glyphosate. Confirmou-se a resistência dos três biótipos pelo controle visual e acúmulo de ácido chiquímico e quínico. A metabolização em AMPA não é considerada mecanismo de resistência da espécie ao glyphosate. Os biótipos resistentes apresentaram maior concentração de ácido salicílico. As progênies obtidas por autofecundação apresentaram fator de resistência para EC50 de 14,37 e 7,04 e para GR50 12,79 e 3,77. / Digitaria insularis ocurrence infestations in annual crop and cases of glyphosate herbicide resistance have increased in recent years, and the facts contributed to make the species one of the most important weeds in Brazil. Therefore, experiments were carried out to confirm the resistance of perennial and vegetatively propagated D. insularis biotypes resistant to glyphosate, as well as to understand the metabolic profile of the herbicide in these plants, to verify if there is alteration in the relative control according to the methods and determine the resistance factor in the progenies obtained by self-fertilized seeds. Three experiments were carried out under greenhouse conditions in a completely randomized design, the first two with eight sourgrass biotypes considered as susceptible and three with suspected resistance to glyphosate herbicide. In the first experiment, the control of the plants at 7, 14, 21 and 28 days after glyphosate application (DAA) was evaluated. In the second experiment, the control was evaluated in the same periods of the first and 72 hours after the application of the herbicide was quantified the accumulation of shiquimic acid and quinic acid, deposition, absorption and translocation of glyphosate, concentration of AMPA, aromatic amino acids (phenylalanine, tyrosine and tryptophan) and salicylic acid. In the third experiment, dose-response curves were conducted with glyphosate at doses of 0; 90; 180; 360; 720; 1440; 2880 and 5760 g e.a. ha-1 , in the progeny of four biotypes, and control and dry mass were evaluated at 21 DAA to obtain the resistance factor. The vegetative propagation method was consistent and did not alter the response of the biotypes in the glyphosate control tests. The resistance of the three biotypes was confirmed by the visual control and accumulation of shikimic and quinic acid. Metabolization in AMPA is not considered a resistance mechanism of the species to glyphosate. Resistant biotypes showed higher concentration of salicylic acid. The progenies obtained by self-fertilization presented a resistance factor for EC50 of 14,37 and 7,04 and for GR50 12,79 and 3,77.

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>

<p>In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical &ldquo / soft template&rdquo / method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm.</p>

Philosophiae Doctor - PhD / In this thesis, I present a simple, sensitive and low cost electrochemical nanobiosensor for quantitative determination of the herbicides glufosinate, glyphosate and its metabolite aminomethylphosphonic acid (AMPA). Firstly, the nanostructured poly(2,5-dimethoxyaniline) (PDMA) materials were synthesized on gold electrode by the electrochemical "template"method using poly(4-styrenesulfonic acid) (PSS) as the dopant and structure-directing molecule. Fourier transform infrared (FTIR) spectroscopy, UV-Vis Spectroscopy, Transmission electron microscopy (TEM) and Scanning electron microscopy (SEM) studies inferred successful doping of the nanostructured PDMA film by PSS and that the template PSS directed the synthesis of both nanotubes and nanoparticles of PDMA with diameters less than 100 nm. / South Africa

El glifosat, N-(fosfonometil) glicina, és un dels herbicides més utilitzats arreu del món a causa de la seva baixa toxicitat i al seu ampli espectre d'aplicació. A conseqüència del gran ús que se'n fa, és necessari monitoritzar aquest compost i el seu principal metabòlit, l'àcid aminometilfosfònic (AMPA), en el medi ambient. S'han descrit diversos mètodes instrumentals basats en cromatografia de gasos (GC) i de líquids (HPLC), sent aquesta darrera l'opció més favorable a causa del caràcter polar dels anàlits. Per assolir nivells de concentració baixos cal, però, la preconcentració dels anàlits.En aquest treball s'estudien diferents alternatives amb aquest objectiu. S'ha avaluat la tècnica de membrana líquida suportada (SLM) on la membrana consisteix en una dissolució orgànica, que conté un transportador (en el nostre cas, un bescanviador d'anions comercial, Aliquat 336), que impregna un suport polimèric microporós que se situa entre dues solucions aquoses: la de càrrega, que conté els anàlits inicialment, i la receptora, on es retenen els anàlits després del seu transport a través de la membrana. Les condicions d'extracció més adequades s'obtenen treballant en medi bàsic amb NaOH on els anàlits estan en forma aniònica i les majors recuperacions s'obtenen amb HCl 0,1 M o NaCl 0,5 M, la qual cosa indica que l'ió clorur és la força impulsora del transport.Un cop dissenyat el sistema, es duen a terme experiments de preconcentració amb dues geometries diferents: un sistema de membrana laminar (LSLM) on recircula la fase receptora i un sistema de fibra buida (HFSLM). Els millors resultats s'obtenen amb el mòdul de fibra buida, amb factors de concentració de 25 i 3 per a glifosat i AMPA, respectivament, fent recircular durant 24 hores 100 ml de solució de càrrega i 4 ml de solució receptora. També s'aplica una tècnica més selectiva, la cromatografia d'afinitat amb ió metàl·lic immobilitzat (IMAC), basada en la interacció entre els anàlits i un metall immobilitzat en una resina a través d'un grup funcional d'aquesta. En aquest estudi s'immobilitza pal·ladi al grup funcional 8-hidroxiquinoleïna de la resina amb matriu acrílica Spheron Oxine 1000 i s'avalua per a l'extracció i preconcentració de glifosat i AMPA. Per a ambdós anàlits l'adsorció és del 100 % i les recuperacions són superiors al 80 % i al 60 % per a glifosat i AMPA, respectivament, utilitzant HCl 0,1 M + NaCl 1 M com a eluent. Aquests resultats es comparen amb els obtinguts amb dues resines més, també carregades amb pal·ladi: Iontosorb Oxin 100, que té el mateix grup funcional però matriu de cel·lulosa, i Spheron Thiol 1000, on el grup funcional és un tiol i la matriu també és acrílica. Per al glifosat els resultats són similars amb totes les resines, però per a l'AMPA la resina Spheron Thiol és la única que proporciona recuperacions superiors al 93 %.Finalment, una altra opció estudiada és l'acoblament de dues columnes de cromatografia líquida (LC-LC). En l'estudi l'objectiu és millorar el mètode existent per a glifosat i AMPA en aigües naturals on el LOD era de 0,25 ug/l. El mètode consisteix en la derivatització precolumna amb el reactiu fluorescent FMOC i l'anàlisi amb l'acoblament LC-LC-fluorescència. Variant lleugerament les condicions de derivatització s'aconsegueix quantificar 0,1 ug/l de glifosat i AMPA. Es fortifiquen aigües naturals amb 0,1, 1 i 10 ug/l dels anàlits per validar el mètode. S'obtenen recuperacions d'entre el 85 % i el 100 %, amb desviacions estàndard relatives inferiors al 8 %. Aplicant una tècnica de preconcentració prèvia a la derivatització i anàlisi utilitzant una resina de bescanvi aniònic, Amberlite IRA-900, es millora la sensibilitat del mètode i s'assoleix un LOD per al glifosat de 0,02 ug/l. / Glyphosate, N-(phosphonomethyl)glycine, is one of the most widely used herbicides in the world due to its low mammal toxicity. Therefore, there is a great interest in the monitoring of this compound and its major metabolite aminomethylphosphonic acid (AMPA), in environmental matrices. A great variety of methods based on gas chromatography (GC) and liquid chromatography (HPLC) have been applied for their determination. HPLC is the most popular option due to the polar nature of both compounds. However, the analysis of these compounds at residue levels requires the use of preconcentration techniques.In this work we have studied different alternatives to this aim. We have evaluated the supported liquid membrane (SLM) technique where the membrane consists of an organic solution, which contains the carrier (in this case a commercial anion exchanger extractant, Aliquat 336), that impregnates a microporous polymeric support placed between two aqueous solutions: the feed solution, which initially contains the analytes, and the stripping solution, where the analytes are retained after their transport through the membrane. The best conditions were achieved with NaOH as feed solution, where the analytes are present in their anionic form and 0.1 M HCl or 0.5 M NaCl as stripping solutions indicating that the chloride ion is the responsible for the transport.Under these chemical conditions some preconcentration experiments were run using two different geometries of the membrane: a laminar membrane system (LSLM) where the stripping solution can be recirculated and a hollow fiber liquid membrane (HFSLM). The best results were obtained for the liquid membrane system in HF configuration, with concentration factors of 25 and 3 for glyphosate and AMPA, respectively, after recirculation during 24 hours of 100 ml of feed solution and 4 ml of stripping solution.A more selective technique is also studied, immobilised metal ion affinity chromatography (IMAC), which is based on the interaction between the analytes and a metal immobilised in a resin through a functional group. In this work we have immobilised palladium through the chelating group 8-hydroxyquinoline of the acrylic resin Spheron Oxine and it has been evaluated for the preconcentration of glyphosate and AMPA. 100 % adsorption has been obtained for both analytes and the recoveries are higher than 80 % and 60 % for glyphosate and AMPA, respectively, using 0.1 M HCl + 1 M NaCl as eluent. These results are compared with the results obtained working with two different resins also charged with palladium: Iontosorb Oxin, which has the same functional group but cellulose matrix, and Spheron Thiol, which a thiol functional group and acrylic matrix. The results for glyphosate are similar with all the resins tested, but for AMPA the best results are obtained with Spheron Thiol with recoveries higher than 93 %.Finally, another option studied is the coupling of two liquid chromatographic columns (LC-LC). In this work the objective is to improve the existing method for the analysis of glyphosate and AMPA in natural waters which had a LOD of 0.25 mg/l. The method consists of the pre-column derivatization with the fluorescent reagent FMOC and the analysis by LC-LC-fluorescence detection. The derivatization step has been slightly modified with the aim of decreasing the limits of quantification of glyphosate and AMPA down to 0.1 mg/l. Different water samples spiked at three concentration levels (0.1, 1, 10 mg/l) were analysed by the improved method yielding recoveries between 85-100 % with relative standard deviations lower than 8 %.Additionally, the potential of an anion-exchange resin, Amberlite&#61650; IRA-900, for preconcentration of glyphosate, previously to the derivatization step, has been investigated. In this way the LOD of the parent compound has been lowered to 0.02 mg/l.

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