Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: In traditional medicine, there is a long-standing culture of combining herbal drugs to increase the therapeutic efficacy. The improved medical action is thought to be due to synergistic interactions between different plant bioactive components. The aim of this study was to test the pharmacological interactions in a medicinal plant combination which consisted of Agathosma crenulata, Dodonaea viscosa and Eucalyptus globulus. The rationale for the analysis of this particular mixture is that it had noteworthy antibacterial activity and exhibited the highest activity out of seven medicinal plant mixtures previously investigated. Using chromatographic analysis, the phytochemistry of the plants was also assessed. The chloroform: methanol (1:1; v/v) extracts or hydo-distilled essential oils (A. crenulata and E. globulus) were screened individually and in combinations (double and triple plant combination) for activity against five respiratory pathogens using a microdilution assay. The antimicrobial interactions in combinations were assessed with the fractional inhibitory concentration (FIC) and the isobolograms. The organic extracts generally showed the highest antimicrobial activity with E. globulus having the highest activity with MIC values below 1 mg ml-1 representing noteworthy activity. The overall activity of the aqueous extracts was poor. The essential oil activity of E. globulus was mostly noteworthy (0.5 to 2 mg ml-1) while A. crenulata essential oil displayed moderate activity (1 to 4 mg ml-1). The ΣFIC values for double combinations (1:1) of A. crenulata with D. viscosa, A. crenulata with E. globulus and D. viscosa with E. globulus were calculated from the minimum inhibitory concentration (MIC) data and the interactions were classified as synergistic, additive, indifferent and antagonistic. The highest synergistic interactions observed were for a 1:1 combination of A. crenulata with E. globulus against K. pneumoniae, S. aureus and B. subtilis with ΣFIC values of 0.07. There was only one incident of antagonism noted in the study for D. viscosa with E. globulus (1:1) against C. neoformans with ΣFIC value of 4.25. The double combinations against selective pathogens (K. pneumoniae, S. aureus and E. coli) were further analysed for interactions using isobolograms. Mostly, the antimicrobial interactions as presented by the isobolograms were congruent with FIC results which further validated the occurrence of relevant antimicrobial interactions in those combinations. The ΣFIC values for triple combinations (1:1:1) revealed mostly synergistic interactions. When the triple combinations were analysed further against certain pathogens based on the predictions of the Design of Experiments software program (MODDE 9.1®), the MIC values remained the same despite the different combinations that were tested Thin layer chromatography (TLC) was used for a quick chemical fingerprinting of the plant extracts. This was followed by a bio-autographic assay. The chemical profiles of the organic extracts and essential oils from two of the study aromatic plants (A. crenulata and E. globulus) were further analysed with liquid chromatography mass spectrometry (LC-MS) and gas chromatography mass spectrometry (GC-MS) respectively. For combined plant extracts, a multivariate data analysis using principal component analysis (PCA) and hierarchical clustering analysis (HCA) was used to determine the relationship of the chemical make-up of combinations with that of individual plant extracts. According to the TLC analysis, E. globulus extracts had more compounds than the other two plants in the study. For the bio-autographic assay, E. globulus and combinations that included this plant showed greater inhibition zones than A. crenulata and D. viscosa. For the LC-MS analysis, PCA and HCA showed a close relationship between A. crenulata with D. viscosa, D. viscosa with E. globulus and the triple combination. Twenty one components were identified in the essential oil of A. crenulata representing 88.83% of the total oil composition. The oil was dominated by oxygen-containing monoterpenes (46.25%). In the essential oil of E. globulus, twenty six compounds were identified making up to 95.62% of the oil composition. Oxygen-containing monoterpenes (32.98%) also dominated the E. globulus essential oil. There was no great variation in essential oil metabolites of the individual plants and their combination as shown by both PCA and HCA. The enhanced in vitro antimicrobial activity and pharmacological interactions (synergy and additivity) in some of the combinations (double and triple) that were tested in this study adds scientific support to the use of medicinal plant combinations in Western Cape traditional medicine. The metabolic profiles of plants in combination might be unique due to interaction of the different plant bioactive molecules and thus result into defined antimicrobial activity. / AFRIKAANSE OPSOMMING: In tradisionele geneeskunde is dit ’n lank bestaande kultuur om kruiemiddels te kombineer om die terapeutiese werking daarvan te verhoog. Dié verbeterde mediese werking word toegeskryf aan die oënskynlik sinergistiese interaksies tussen verskillende bioaktiewe plantkomponente. Die doel van hierdie studie was om die farmakologiese interaksies in medisinale plantkombinasies van Agathosma crenulata, Dodonaea viscosa en Eucalyptus globulus te bestudeer. Daar is op die ontleding van hierdie spesifieke mengsel besluit omdat dit oor beduidende antibakteriese waarde beskik en omdat dit uit sewe medisinale plantmengsels wat voorheen bestudeer is, as die doeltreffendste een aangewys is. Die fitochemie van die plante is ook met behulp van chromatografiese ontleding beoordeel. Deur middel van ’n mikroverdunningstoets is die chloroform:metanol- (1:1; v/v-)ekstrakte of hidrogedistilleerde vlugtige olies (A. crenulata en E. globulus) individueel sowel as in kombinasie (dubbele en drievoudige plantkombinasies) nagegaan vir hul werking met betrekking tot vyf respiratoriese patogene. Die gekombineerde antimikrobiese interaksies is met behulp van fraksioneel stremmende konsentrasie (FIC) en isobologramme ondersoek. Die organiese ekstrakte het oor die algemeen die meeste antimikrobiese aktiwiteit by E. globulus getoon, met MIC-waardes onder 1 mg ml-1 wat as noemenswaardige aktiwiteit beskou is. Die algehele aktiwiteit van die waterekstrakte was swak. Die vlugtige-olieaktiwiteit van E. globulus was merendeels noemenswaardig (0,5 tot 2 mg ml-1), terwyl die vlugtige olie van A. crenulata matige aktiwiteit getoon het (1 tot 4 mg ml-1). Die ΣFIC-waardes vir dubbelkombinasies (1:1) van A. crenulata en D. viscosa, A. crenulata en E. globulus, en D. viscosa en E. globulus is uit die minimum stremmende konsentrasie (MIC) bereken en die interaksies is as sinergisties, additief, neutraal en antagonisties geklassifiseer. Die sterkste sinergistiese interaksies is by ’n 1:1-kombinasie van A. crenulata en E. globulus met betrekking tot K. pneumoniae, S. aureus en B. subtilis opgemerk, met ΣFIC-waardes van 0,07. Die studie het slegs een geval van antagonisme opgelewer, naamlik by D. viscosa en E. globulus (1:1) met betrekking tot C. neoformans, wat ’n ΣFIC-waarde van 4,25 geregistreer het. Die werking van die dubbelkombinasies met betrekking tot gekose patogene (K. pneumoniae, S. aureus en E. coli) is voorts met behulp van isobologramme vir interaksies nagegaan. Die antimikrobiese interaksies wat uit die isobologramme geblyk het, was meestal in pas met FIC-resultate, wat die bestaan van tersaaklike antimikrobiese interaksies in daardie kombinasies verder bevestig het. Die ΣFIC-waardes vir die drievoudige kombinasies (1:1:1) het meestal sinergistiese interaksies aan die lig gebring. Toe die drievoudige kombinasies verder op grond van die voorspellings van die sagteware Design of Experiments (MODDE 9.1®) met betrekking tot sekere patogene ontleed is, het die MIC-waardes onveranderd gebly, ondanks verskillende toetskombinasies. Dunlaagchromatografie (TLC) is vir ’n vinnige chemiese ontleding van die plantekstrakte gebruik en is gevolg deur ’n bio-outografiese toets. Die chemiese profiele van die organiese ekstrakte en vlugtige olies van twee van die aromatiese plante in die studie (A. crenulata en E. globulus) is verder met vloeistofchromatografie-massaspektrometrie (LC-MS) en gaschromatografie-massaspektrometrie (GC-MS) onderskeidelik ontleed. Vir gekombineerde plantekstrakte is veelveranderlike-ontleding in die vorm van hoofkomponentontleding (PCA) en hiërargiese groepsontleding (HCA) gebruik om die verhouding van die chemiese samestelling van kombinasies in vergelyking met dié van individuele plantekstrakte te bepaal. Volgens die TLC-ontleding beskik E. globulus-ekstrakte oor meer verbindings as die ander twee plante in die studie. Vir die bio-outografiese toets het E. globulus en kombinasies daarmee groter stremmingsones as A. crenulata en D. viscosa getoon. In die LC-MS-ontleding het PCA en HCA op ’n hegte verhouding tussen A. crenulata en D. viscosa, D. viscosa en E. globulus, en die drievoudige kombinasie daarvan gedui. Een-en-twintig komponente is in die vlugtige olie van A. crenulata gevind, wat 88,83% van die algehele oliesamestelling uitmaak. Die olie is deur suurstofhoudende monoterpene (46,25%) oorheers. Die vlugtige olie van E. globulus het 26 verbindings opgelewer, wat 95,62% van die oliesamestelling uitmaak. Suurstofhoudende monoterpene (32,98%) het ook die vlugtige olie van E. globulus oorheers. Nóg PCA nóg HCA het op enige beduidende variasie in die metaboliete van die vlugtige olies van die individuele plante en hul kombinasies gedui. Die verhoogde in vitro- antimikrobiese aktiwiteit en farmakologiese interaksies (sinergie en additiwiteit) in van die kombinasies (dubbel én drievoudig) wat in hierdie studie getoets is, bied wetenskaplike stawing vir die gebruik van medisinale plantkombinasies in Wes-Kaapse tradisionele geneeskunde. Die metaboliese profiele van plantkombinasies kan verander weens die interaksie van die verskillende bioaktiewe plantmolekules, en kan baie bepaalde antimikrobiese aktiwiteit tot gevolg hê.

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2007. / In this thesis the main capillary electrodriven chromatographic techniques (i.e. Capillary Electrochromatography CEC, Micellar Electrokinetic Chromatography MEKC and Microemulsion Electrokinetic Chromatography MEEKC) were compared in terms of column manufacturing, fundamental chromatographic performance, and some applications were developed. The first stage of this thesis aimed at developing improved packed and open tubular CEC columns. For the manufacturing of packed CEC columns, the frit-burning step proved of critical importance, together with the slow build-up of the packed bed. The making of open tubular columns is a relatively simple, "one pot" sol-gel reaction taking place in mild conditions. The nature of the gel and the resulting selectivity of the column could easily be changed by changing the precursors. In a second stage of this thesis the packed and open tubular CEC columns were evaluated chromatographically and compared with the results obtained by MEKC and MEEKC. All electrodriven separation techniques showed high efficiencies. The selectivity proved easier to tune with sol-gel chemistry for the making of open tubular columns. Resolution is acceptable for packed CEC, MEKC and MEEKC. For peak capacity, CEC has the advantage of a practically non-limited elution time, while MEKC and MEEKC suffer of the drawback of the existence of an elution window which is limited in time by the elution of the micelles. Some applications were developed in this study on open tubular CEC columns and for the packed CEC columns. Various sugars derivatized with 9- aminopyrene-1,4,6-trisulfonic acid (APTS) could be separated with open tubular CEC, using an octyl, amino or cyano stationary phase. Open tubular columns containing α, β and γ cyclodextrins attached to the stationary phase were developed. This approach proved promising for the separation of positional isomers. A method was developed for the analyses of a mixture of carbamates and for several steroids with packed column CEC directly coupled with MS.

Thesis (PhD)--Stellenbosch University, 2015. / ENGLISH ABSTRACT: Anthocyanins are naturally occurring pigments responsible for the colour of many natural products, including grapes and wine. These pigments are important to the food industry and have been recognised for their nutritional value since they play an important role in the reduced risk of various chronic diseases in humans. Anthocyanins also play an important role in the aesthetic perception and quality of red wine. However, due to the large structural diversity of grape-derived anthocyanins and the many derivatives formed from these during wine ageing, the accurate analysis of wine pigments is extremely challenging. Reversed-phase liquid chromatography (RP-LC) is mostly used for anthocyanin analysis, although the technique often provides insufficient resolving power for complex mixtures of anthocyanins. In addition, the lack of commercially available standards and identical mass spectral characteristics hampers identification of these compounds. The coupling of multiple orthogonal separation systems in comprehensive 2-dimensional liquid chromatography (LC×LC) offers a more powerful approach for the separation of complex mixtures. The current work therefore focussed on exploring the potential of LC×LC for the improved analysis of anthocyanins and derived pigments in natural products and wine. The first part of this work focussed on developing a hydrophilic interaction chromatography (HILIC) method as an alternative to RP-LC for the anthocyanin analysis. Following extensive optimisation, the method proved suitable for the analysis of a diverse range of anthocyanins in natural products. Significantly, it also showed alternative selectivity compared to RP-LC. The optimised HILIC method was then used in combination with RP-LC to develop an off-line LC×LC approach for anthocyanins. For this purpose, half-minute fractions of the HILIC effluent were collected and reinjected onto a RP-LC column. The off-line HILIC×RP-LC method demonstrated exceptionally high resolving power, as measured in terms of the practical peak capacity, with many compounds separated in two dimensions that co-eluted in 1-dimensional HPLC. Interestingly, group-type separation was also observed based on the degree and/or nature of glycosylation and acylation of anthocyanins. In the final part of the work, a systematic approach was used for the development and optimisation of and on-line HILIC×RP-LC method by using a 10-port switching valve to automatically transfer fractions between the two columns. This method was then coupled to high resolution mass spectrometry (MS) to allow the detailed investigation of anthocyanins and derived products in wine. Ninety four pigments were identified in one- and six-year old Pinotage wines based on HILIC×RPLC separation in combination with accurate mass MS data and fragmentation information. Significant differences in especially the content of derived pigments were observed between the wines. In summary, the methods developed in this work provide the means to improve anthocyanin analysis, and therefore also show promise for the detailed investigation of these important compounds and their alteration in natural products and their derived commodities. / AFRIKAANSE OPSOMMING: Antosianiene is natuurlike pigmente wat verantwoordelik is vir die kleur van baie natuurlike produkte, insluitende dié van druiwe en wyn. Hierdie pigmente is belangrik vir die voedsel industrie en word gereken vir hul voedingswaarde aangesien hulle 'n belangrike rol speel in die verlaagde risiko van verskeie chroniese siektes onder die mens. Antosianiene speel ook 'n belangrike rol in die estetiese persepsie en kwaliteit van rooiwyn. Desnieteenstaande, as gevolg van die groot strukturele diversiteit van druifgeproduseerde antosianiene en die vele chemiese afgeleides wat uit hulle gevorm kan word tydens wyn bereiding en veroudering, is die akkurate analise van natuurlike wyn-pigmente uiters uitdagend. Omgekeerde-fase vloeistofchromatografie (RP-LC) word meestal gebruik vir die analise van antosianiene. Dié tegniek bied egter dikwels onvoldoende skeidingsvermoë vir komplekse mengsels van antosianiene en verwante molekules. Verder belemmer die onbeskikbaarheid van kommersiële standaarde en identiese massa spektrale eienskappe die identifikasie van hierdie verbindings. Die kombinasie van verskillende ortogonale skeidings meganismes in omvattende 2- dimensionele vloeistofchromatografie (LC×LC) bied egter 'n baie kragtiger benadering vir die skeiding van komplekse mengsels. Die huidige werk fokus dus op die ontginning van die potensiaal van LC×LC vir die verbeterde ontleding van antosianiene en verwante afgeleide pigmente in natuurlike produkte en wyn. Die eerste deel van hierdie werk het gefokus op die ontwikkeling van 'n hidrofiliese interaksie chromatografiese (HILIC) metode as ʼn alternatief vir RP-LC analise van antosianiene. Na uitgebreide optimisering, is gevind dat die metode geskik is vir die ontleding van 'n verskeidenheid van antosianiene in natuurlike produkte. Van groot belang is dat dit ook alternatiewe selektiwiteit in vergelyking met RP-LC demonstreer. Hierdie geoptimiseerde HILIC metode word dan voorts gebruik in kombinasie met RP-LC vir die ontwikkeling van ʼn af-lyn LC×LC benadering vir die analise van antosianiene. Hiervoor is half-minuut fraksies van die HILIC uitvloei opgevang en her-ingespuit op 'n RP-LC kolom. Dié af-lyn HILIC×RP-LC metode toon buitengewoon hoë skeidingsvermoë, gemeet in terme van die bereikbare praktiese piek kapasiteit, met baie verbindings wat geskei is in die twee dimensies wat saam elueer in 1-dimensionele HPLC. Interessant genoeg is groep-tipe skeiding ook waargeneem gebaseer op die graad en / of aard van glukosilasie en asilering van die antosianiene. In die laaste deel van die werk, is 'n sistematiese benadering gevolg vir die ontwikkeling en optimisering van ʼn aan-lyn HILIC×RP-LC deur gebruik te maak van 'n 10-poort oorskakelingsklep wat fraksies outomaties oordra tussen die twee kolomme. Die bogenoemde metode is ook verder gekoppel aan hoë resolusie massaspektrometrie (HR-MS) om ʼn gedetailleerde ondersoek van antosianiene en hulle afgeleide verbindings in wyn moontlik te maak. Vier en negentig pigmente is in een- en ses jaar oue Pinotage wyne geïdentifiseer gebaseer op HILIC×RP-LC skeiding in kombinasie met akkurate massa MS data en fragmentasie inligting. Beduidende verskille in veral die inhoud van antosianien-afgeleide pigmente is tussen die wyne waargeneem. Ter samevatting, die metodes ontwikkel in hierdie werk baan die weg om antosianien ontleding te verbeter en stel gevolglik die moontlikheid van selfs meer gedetailleerde studies van hierdie belangrike verbindings in natuurlike produkte in die vooruitsig.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The method utilizes both cation and anion concentrator columns in parallel as a preconcentration system. The preconcentrator system is loaded using a reagent delivery module operated for a specific time at a preset flow rate. Total injection volumes of 2-5 ml are routinely used. Various chromatograms are discussed along with detailed information concerning detection limits for sodium and chloride, the system operating conditions, and the solutions to other pitfalls which have arisen during the course of this work.

Orientador: Denide Fecchio / Coorientador: Camila Renata Côrrea / Banca: Daniela Souza Ferreira / Banca: Giuseppina Pace Pereira Lima / Banca: Mariana Gobbo Braz / Banca: Willian Fernando zambuzzi / Resumo: Os compostos bioativos do arroz variam de acordo com a variedade e condições de cultivo. Componentes lipossolúvies como γ-orizanol, tocoferóis, tocotrienóis, carotenóides e ácidos graxos foram analisados em variedades de arroz integral, integral açucarado, vermelho e negro, utilizando métodos estabelecidos de cromatografia líquida de alta pressão e cromatografia gasosa. Todas as amostras também foram submetidas a análise por cromatografia líquida acoplada a espectrometria de massa (LTQ-Orbitrap XL), para identificar a abundância iônica [M-H]- de γ-orizanol, variando de m/z 573.3949 a 617.4211. O maior conteúdo de tocoferóis (α-, 1.5; γ-, 0.5 mg/100 g) e carotenóides (luteína 244; trans-β caroteno 25 μg/100 g) foram observados no arroz negro; tocotrienóis (α-, 0.07; γ-, 0.14 mg/100 g) em arroz vermelho e γ-orizanol (115 mg/100 g) no arroz integral açucarado. Em todas as amostras de arroz integral coloridas, os principais ácidos graxos encontrados foram palmítico (16:0), oleico (18:1n-9) e linoleico (18:2n-6). A análise dos componentes de γ-orizanol por espectrometria de massa permitiu identificar 3, 10, 8, e 8 álcoois triterpenóides ou esteril ferulatos nas amostras integral, integral açucarado, vermelho e negro, respectivamente. Estas identificações dos componentes de γ-orizanol, assim como, a concentração dos compostos bioativos, pode levar a elucidação das funções biológicas de cada componente à nível molecular. O consumo de amostras de arroz integral colorido, ricas em compostos bioativos benéficos, pode representar uma interessante estratégia dietética para melhoria da saúde / Abstract: Bioactive components in rice vary depending on the variety and growing condition. Fat-soluble components such as γ-oryzanol, tocopherols, tocotrienols, carotenoids and fatty acids were analyzed in brown, sugary brown, red and black rice varieties using established high-performance liquid chromatography (HPLC) and GC methodologies. In addition, these colored rice varieties were further analyzed using a high-resolution liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) (LTQ-Orbitrap XL) to identify the [M-H]- ions of γ-oryzanol, ranging from m/z 573.3949 to 617.4211. The highest content of tocopherols (α-, 1.5; γ-, 0.5 mg/100 g) and carotenoids (lutein 244; trans-β carotene 25 μg/100 g) were observed in black rice; tocotrienols (α-, 0.07; γ-, 0.14 mg/100 g) in red rice, and γ-oryzanol (115 mg/100 g) in sugary brown rice. In all colored rice varieties, the major fatty acids were palmitic (16:0), oleic (18:1n-9), and linoleic (18:2n-6) acids. When the γ-oryzanol components were further analyzed by LC-MS/MS, 3, 10, 8, and 8 triterpene alcohols or sterol ferulates were identified in brown, sugary brown, red, and black rice varieties, respectively. Such structural identification can lead to the elucidation of biological function of each component at the molecular level. Consumption of colored rice rich in beneficial bioactive compounds may be a useful dietary strategy for achieving optimal health / Doutor

Expanded bed chromatography using ion-exchange media is a powerful first step in purification processes. Expanded bed chromatography can be used to extract components from complex and viscous solution. This can be achieved because of the void created between adsorbent particles where as in packed bed chromatography, the adsorbent is too compact and dense for a complex feed stock to flow through. Expanded bed chromatography was used to purify bovine serum albumin (BSA) from chicken egg white (CEW). The high viscosity of CEW presents a unique challenge for efficient large-scale protein purification. This project aimed to optimize and evaluate a separation method that is believed to be particularly suitable for high viscosity solutions: expanded-bed ion exchange chromatography. The BSA was admixed into the CEW and the solution was pumped through the column for purification. The media used in the column was Streamline DEAE which is an anion-exchanger. The yield obtained was 85% and the purity was 57%. A mathematical model to understand and predict the behavior of expanded bed chromatography was developed to provide an estimation of the breakthrough curves obtained for BSA. A small sized porous dense adsorbent was also synthesized to enhance the purification process. This zirconia-based adsorbent allows use of higher flow velocities that is a key factor when working with viscous fluids such as chicken egg white.

"Expanded Bed Chromatography (EBC) is rapidly becoming the preferred choice for initial product recovery from crude process streams as it enables direct protein recovery from culture broths after appropriate dilution. However, the process is time intensive, and there are still some difficulties with very high cell density cultures in the 500 g/L range. Problems include in-column clogging and poor column efficiency. With the development of a new prototype EBC column capable of product recovery from undiluted culture broth, it is proposed in this study to combine the fermentation with EBC recovery. This strategy was tested using a wild type, non-producing strain of Pichia pastoris. Culture broths were spiked with 200 mg/L lysozyme to mimic an actual production fermentation. Key parameters for the process were identified and tested independently to better assess system performance: potential toxic effects of the resin on the culture, nutrient deprivation of the cells as they pass through the column and binding of the target protein from whole broth. The cation exchanger had a negligible effect on cell proliferation in shake flask studies using YNB Medium. Isolation of the culture from the fermenter for up to two hours appeared to have minimal effect on overall cell viability and the ability to metabolize methanol. The dynamic binding capacity for lysozyme was 50 mg/mL in buffer, and 20 mg/mL in undiluted fermentation broth containing 500 g/L cells. When harvested undiluted fermentation broth was allowed to recirculate through the EBC column, the binding capacity was increased to 30 mg/mL. The combination of the fermentation and recovery process allowed for a binding capacity of 30-40 mg/mL, with no dramatic effects on biomass accumulation or metabolic rate."

Made available in DSpace on 2016-12-23T14:04:27Z (GMT). No. of bitstreams: 1 Andreia do Rozario.pdf: 4502338 bytes, checksum: b9ac291e79af94761b6c6b25dc856c36 (MD5) Previous issue date: 2012-08-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O aumento do uso de agrotóxicos no Brasil tem causado muitas preocupações, devido aos problemas ambientais e de saúde que podem causar. Muitos desses produtos não são eficientemente removidos das águas por tratamento convencional, sendo necessárias alternativas que os removam das águas de abastecimento. Uma das opções é o uso do carvão ativado granular (CAG) em leitos fixos, pois devido a alta eficiência para remoção de microcontaminantes e facilidade de operação, essa tecnologia é uma das mais efetivas e confiáveis para o tratamento de água. O objetivo desse trabalho foi avaliar, através do sistema Testes Rápidos de Colunas em Pequena Escala (ou RSSCT Rapid Small-Scale Column Tests), a capacidade de adsorção do CAG na remoção do 2,4-D em amostras de água destilada/deionizada (ADD) e filtrada proveniente de estação de tratamento de água (AFE) fortificadas (apenas com 2,4-D ou associado a 2,4,5-T ou atrazina). Os agrotóxicos foram detectados e quantificados através de cromatografia líquida de alta eficiência (CLAE), em metodologia adaptada e adequadamente validada. Foram realizados oito ensaios com leitos fixos em série, onde se variou o tipo de água utilizada e a taxa de aplicação superficial. As capacidades de adsorção obtidas em amostras de água fortificadas apenas com o 2,4-D apresentaram valores superiores aos obtidos a partir de isotermas. Além disso, a matéria orgânica natural (MON) exerceu grande influência na adsorção do 2,4-D, diminuindo sua capacidade de adsorção. Nos efluentes dos ensaios realizados com AFE fortificadas apenas com 2,4-D verificou-se, através dos valores das absorbâncias a 254 nm, a remoção de MON pelo CAG. Além disso, verificou-se a adsorção preferencial de agrotóxicos hidrofóbicos (2,4,5-T e atrazina) perante o 2,4-D, pois em todos os ensaios com amostras de águas fortificadas com 2,4-D associado a 2,4,5-T ou atrazina, verificouse uma diminuição na capacidade de adsorção do CAG / The increased use of pesticides in Brazil has caused many concerns due to environmental and health problems they can cause. Many of these products are not efficiently removed by conventional treatment of water, requiring alternatives that remove the water supply. One option is the use of granular activated carbon (GAC) in fixed beds, because due to the high efficiency removal of microcontaminants and ease of operation, this technology is one of the most effective and reliable water treatment. The aim of this study was to evaluate, through the Rapid Tests in Small Scale Column (RSSCT), the adsorption capacity of GAC in removing 2,4-D in samples of distilled / deionized (DDW) and filtered from the water treatment plant (FWTP) fortified (only with 2,4-D or associated with atrazina or 2,4,5-T). Pesticides were detected and quantified using high performance liquid chromatography (HPLC), the methodology adapted and properly validated. Eight tests were performed with fixed beds in series, which varied the type of water used and the rate of surface application. The adsorption capacities obtained from water samples spiked with only 2.4-D had higher values than those obtained from isotherms. Furthermore, natural organic matter (NOM) had a great influence on the adsorption of 2,4-D, decreasing its adsorption capacity. In the tests performed with effluent spiked with only FWTP with 2,4-D was observed by absorbance values at 254 nm, the removal of the MON by CAG. Furthermore, there was a preferential adsorption of hydrophobic pesticides (2,4,5-T, and atrazine) to the 2,4-D, since in all tests water samples spiked with 2,4-D associated with 2,4,5-T or atrazine, there was a decrease in the adsorption capacity of the CAG

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-09T11:39:47Z No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) / Made available in DSpace on 2017-05-09T11:39:47Z (GMT). No. of bitstreams: 1 2012 - Filipe Arantes Furtado.pdf: 4817236 bytes, checksum: 027c11b973e31fc0617693a998446e3e (MD5) Previous issue date: 2012-07-26 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / The main objective of this work was the development of a methodoly using the Solid Phase Microextraction (SPME) on determinations of thermodynamic equilibrium data of liquid and polymeric mixtures. Three methodologies were proposed for determination of infinite dilution activity coefficient of solutes in liquid mixtures (??). The ?? values were determined for 9 hydrocarbons in the solvent furfural at temperatures of 25, 35 and 45 ?C. The liquid-gas partition coefficients were also determined in each studied temperature. On the experiments involving liquid mixtures, high sorption of solvent was observed, which may lead to swelling the polymer coating phase. Statistical tests were conducted after each experiments to measure possible damages on fiber coatings. There was also proposed a methodology using the SPME to determine the Flory Huggins parameter of the nine hydrocarbons used as solutes in polydimethylsiloxane (PDMS) and polyacrylate (PA). The Flory parameter were determined at temperature range of 25 to 80 ?C for the PDMS and 50 to 90 ?C for the PA. The proposed methodologies were evaluated through comparison of the obtained data with literature. All the results agreed with literature data. The Hildebrandt solubility parameter for PA was not available on literature and was determined on these experiments for the first time / O principal objetivo deste trabalho foi o desenvolvimento de uma nova metodologia para determina??o de dados de equil?brio termodin?mico em misturas l?quidas e polim?ricas. Tr?s metodologias foram propostas utilizando a Microextra??o em Fase S?lida (SPME) para determina??o dos coeficientes de atividade em dilui??o infinita (??) de sistemas l?quidos. Os valores de ?? de 9 hidrocarbonetos foram determinados em furfural nas temperaturas de 25, 35 e 45 ?C. Foram determinados valores de coeficiente de parti??o l?quid-g?s (KLg) em cada uma das temperaturas estudadas. Nos experimentos envolvendo as misturas l?quidas, foi observada uma alta taxa de sor??o de solvente podendo ocasionar o inchamento e poss?vel quebramento das fibras de SPME. Para verificar o poss?vel inchamento, foram conduzidos testes estat?sticos antes e depois de cada amostragem. Foi proposto ainda uma metodologia para determinar os par?metros de Flory em polidimetilsiloxano (PDMS) e poliacrilato (PA) utilizando a SPME. Nesse caso, os mesmos 9 hidrocarbonetos tiveram seus par?metros de Flory determinados na faixa de temperatura 25 a 80 ?C para o PDMS e de 50 a 90 ?C para o PA. As metodologias foram avaliadas atrav?s da compara??o dos dados obtidos com dados da literatura. Todos os resultados foram satisfat?rios, sendo ainda obtidos os valores dos par?metros de solubilidade de Hildebrandt, que para o poliacrilato, eram inexistentes na literatura