Made available in DSpace on 2017-07-21T18:53:23Z (GMT). No. of bitstreams: 1 Conclusoes.pdf: 25119 bytes, checksum: cc97815b6091a5ebb507d0a3dc17c116 (MD5) Previous issue date: 2007-09-19 / The apple consumption can contribute in the improvement of the health and well-being by reducing the risk the diseases such as cancer, asthma, diabetes type II and cardiovascular diseases. Scientific evidences indicate that the polyphenols, compounds with high antioxidant activity, are the responsible for this effect. These compounds can vary between varieties, in function of the climate and the cultural treatments. In Brazil little was researched in relation to these constituent in apples, this study presents in one first moment, the analysis of different varieties, considering the whole fruit and their parts, with elaboration of a classification with low and high values. The biggest phenol concentration and antioxidant activity was found in the epicarp. In varieties with different intensities of red pigmentation, the phenolics compounds content was similar, however the antioxidant potential was different. In one second moment the evaluation occurred during the juice and apple wine processing and the responsible factors for the loss of phenols were the enzymatic oxidation and the despectinization. The third moment was reserved for the apple pomace flour that presented high content of polyphenols and antioxidant activity. The results of this study demonstrate that Brazilian apples are fruits with high antioxidant activity. Moreover, apple products can be potent antioxidant sources, since that inhibit the browning enzymatic reaction. / O consumo de maçãs pode contribuir na melhoria da saúde e bem-estar pela prevenção de doenças como câncer, asma, diabetes tipo II e doenças cardiovasculares. Evidências científicas indicam que os polifenóis, compostos com elevada atividade antioxidante, são os responsáveis por este efeito. Estes compostos podem variar entre as cultivares, em função do clima e das condições culturais. Como no Brasil pouco foi pesquisado em relação a esses constituintes nas maçãs, este estudo apresenta em um primeiro momento, a análise de diferentes cultivares, tanto na fruta inteira quanto em suas partes, com obtenção de uma classificação com resultados baixos e elevados. O epicarpo foi a parte da fruta com as maiores concentrações de fenóis e de poder antioxidante. Em cultivares com diferentes intensidades de pigmentação vermelha os teores de compostos fenólicos foram semelhantes, porém a atividade antioxidante foi diferente. No segundo momento a avaliação ocorreu durante o processamento de sucos e fermentados e os fatores responsáveis pela perda de fenóis foram a oxidação enzimática e a despectinização. O terceiro momento foi reservado para as amostras de farinha de bagaço de maçã que apresentaram altos teores de compostos fenólicos e de atividade antioxidante. Os resultados desse estudo demonstram que as maçãs brasileiras são,em grande parte, frutas com elevado potencial antioxidante. Além disso, produtos de maçãs podem ser boas fontes de compostos fenólicos antioxidantes, desde que inibidores do escurecimento enzimático estejam presentes.

Regulações ambientais cada vez mais rigorosas em relação ao gerenciamento dos resíduos orgânicos estão impelindo a indústria para uma maior sustentabilidade no sentido de melhorar a relação beneficio/custo e também atender a demanda dos clientes. A valorização dos resíduos orgânicos é uma das áreas de investigação atuais que tem atraído grande atenção nos últimos anos como uma alternativa potencial à eliminação de uma vasta gama de resíduos em aterros sanitários. Os resíduos orgânicos como o lodo de esgoto têm sido encarados como um recurso com um potencial significativo para ser empregado como matéria-prima para a produção de vários tipos de produtos, materiais e combustíveis. Este estudo tem como objetivo fornecer subsídios sobre o potencial de uso de lodo de esgoto para produzir carvões ativados e novos materiais adsorventes misturando com diferentes materiais polissiloxanos para adsorção de poluentes orgânicos a partir de soluções aquosas. Os materiais adsorventes foram caracterizados por varias técnicas analíticas e funcionais e utilizados na adsorção de diclofenaco (DCF) , nimesulida (NM) e alguns compostos fenólicos a partir de soluções aquosas Esta tese visa contribuir em (i) comparar os métodos de pirólise (pirólise convencional e aquecimento assistido por micro-ondas) na preparação de carvões ativados a partir de lodo de esgoto. Para isso foi aplicado um planejamento experimental e metodologia de superfície de resposta no sentido de determinar quais as variáveis dos dois processos são as que influenciam na qualidade do carvão produzido; (ii) a combinação de lodo de esgoto com polissiloxanos para preparar adsorventes para adsorção de fármacos a partir de soluções aquosas por processos de adsorção. Os achados gerais desta tese mostraram (i) que ambos os métodos de pirólise produzem carvões ativados com elevadas porosidades e áreas superficiais; (ii) demonstrou-se também que lodo de esgoto pode ser um excelente precursor para a preparação de carvões ativados e que pode com sucesso ser combinado com outros precursores (como polissiloxanos) a fim de se obter novos materiais com diferentes funcionalidades e características; (iii) foi demonstrado que os carvões ativados, híbridos e materiais compósitos desenvolvidos durante o presente estudo são ótimos adsorventes, especialmente para a remoção de diclofenaco DCF e NM a partir de solução aquosa e; (iv) tanto por microondas ou por pirólise convencional, é possível desenvolver CAs de lodo de esgoto com alta eficiência para a remoção de compostos fenólicos em comparação com outros tipos de CAs relatados na literatura. Estes resultados indicam que o lodo de esgoto e polissiloxanos têm grande potencial como precursores para a preparação de materiais adsorventes para o tratamento de água poluída por compostos orgânicos. / Increasingly tighter regulations regarding organic waste are pushing the manufacturing industry toward higher sustainability to improve cost-effectiveness and meet customers’ demand. Organic waste valorisation is one of the current research areas that have attracted a great deal of attention over the past few years as a potential alternative to the disposal of a wide range of residues in landfill sites. Bio-waste like sewage sludge emerged as a resource with a significant potential to be employed as a raw material for the production of chemicals, materials and fuels given its abundant volumes generated globally. This study aims at providing insights into the potential of the use of the sewage sludge to produce activated carbons (ACs) and novel adsorbent materials mixing with different polysiloxanes materials for adsorption of organic pollutants from aqueous solutions. The characterization of adsorbents were achieved by several analytical and functional techniques and used for adsorption of diclofenac (DCF) and nimesulide (NM) from aqueous solutions. The novelties of the present study are (i) to compare both pyrolysis methods (conventional pyrolysis and microwave assisted heating) for preparation of activated carbons from sewage sludge for that It was applied an experimental design and response surface methodology were used for the preparation and comparison of activated carbon produced by both methods, conventional furnace and microwave; (ii) the combination of sewage sludge with polysiloxanes to prepare adsorbents to uptake pharmaceuticals and phenolic compounds from aqueous solutions by adsorption processes. The general findings of this thesis showed (i) that both methods of pyrolysis produce very good activated carbons from sewage sludge with high specific surface areas and high developed porosities; (ii) It was also shown that the sewage sludge can be an excellent precursor to prepare activated carbons and novels materials by mixing it with other precursors such polysiloxanes; (iii) It was shown that the activated carbons, hybrids and composites materials developed during the present study are good adsorbents, especially for the removal of a model diclofenac (DCF) and nimesulide (NM) from aqueous solution and; (iv) that by microwave and conventional pyrolysis it is possible to develop sludge-ACs with very high efficiency for phenolic compounds compared with others kind of ACs reported in literature. These results indicate that sewage sludge and polysiloxanes have great potential as precursors for preparation of adsorbent materials for water treatment polluted by organic pollutants compounds.

A própolis é uma substância resinosa, formada por produtos coletados de plantas e substâncias produzidas pelas abelhas, cuja textura e coloração varia dependendo da fonte de coleta e respectiva fenologia. É utilizada na colméia para diversas finalidades: vedar aberturas, forrar a entrada da colméia e envolver invasores. O interesse por própolis tem crescido muito, devido à comprovação experimental de suas atividades biológicas, tais como citotóxica, anti-herpes, anti-HIV, antitumoral, antimicrobiana e antioxidante. A composição química da própolis é complexa, compreendendo, além de cera de abelha, flavonóides, ácidos fenólicos, terpenóides, substâncias voláteis, entre outros constituintes. A composição depende de vários fatores, principalmente da região onde é produzida. Neste trabalho, estabeleceu-se o perfil químico de amostras de própolis brasileiras, baseando-se nos teores de substâncias fenólicas totais, flavonóides totais e ceras de amostras de distintas regiões do território brasileiro: Ponta Grossa (PR), Bauru e Pariquera-Açu (SP), Lavras e Mira Bela (MG), Pirenópolis (GO), Cabo Verde (BA), Maceió (AL) e Picos (PI). Os teores de fenóis totais foram determinados pelo no método de Folin Ciocalteau, utilizando-se ácido p-cumárico como referência. A dosagem de flavonóides totais baseou-se em dois métodos espectrofotométricos complementares: cloreto de alumínio e dinitrofenil-hidrazina, usando-se quercetina e pinocembrina, respectivamente, como referências. Os teores de ceras foram obtidos por extração com clorofórmio, tratamento com metanol e pesagem do resíduo. Os resultados demonstraram grande diversidade química entre as amostras estudadas, inclusive entre amostras do mesmo estado. Tal é o caso das amostras de Lavras e Mira Bela, e Bauru e Pariquera-Açu. Os teores de fenóis totais variaram de 0,91% a 41,63%, sendo o maior percentual referente à amostra de própolis vermelha (Maceió). Esses resultados são superiores aos obtidos com própolis do Uruguai, Argentina, Paraguai, China e países da Europa, e também de própolis verde brasileira. Os valores obtidos para flavonóides totais variaram entre 0,31% e 4,43%, valores próximos aos encontrados por outros pesquisadores de própolis brasileiras, porém inferiores aos relatados para própolis européia, que variam entre 1,1% e 22,3%. Os teores de ceras determinados, variando entre 5,37% e 45,88%, são superiores aos relatados para outras amostras de própolis brasileiras, sendo comparáveis apenas às própolis chinesas, cujo teor é de aproximadamente 30%. Com base nos teores dosados, foi feita análise de componentes principais (PCA). As amostras de Maceió, Cabo Verde, Pirenópolis e Bauru emergiram isoladamente das demais. Pariquera-Açu e Mira Bela sobressaíram-se no outro extremo do gráfico, devido a baixos teores de compostos fenólicos e altos índices de ceras. As amostras de Picos, Lavras e Ponta Grossa agruparam-se em função de teores de fenóis totais expressivos e de ceras relativamente altos. Foram analisadas as frações clorofórmicas e metanólicas de todas as amostras por HPLC-MS e CG-EM. Essas análises revelaram que as amostras de Bauru, Lavras e Cabo Verde têm composição típica de própolis verde, com muitos fenilpropanóides prenilados e derivados de ácido cafeoilquínico. A composição da própolis de Maceió diferiu muito das demais, incluindo a presença de chalconas. Tais substâncias nunca foram relatadas em própolis anteriormente. As própolis de Pirenópolis e Picos assemelham-se pela presença de muitos flavonóides glicosilados, substâncias nunca reportadas anteriormente para própolis. As amostras de Ponta Grossa, Pariquera-Açu e Mira Bela têm perfil químico intermediário entre a própolis verde e própolis com flavonóides glicosilados. Essas afinidades químicas ficaram bem evidenciadas por meio de análise de agrupamento, usando-se as substâncias identificadas como variáveis e o método de agrupamento UPGMA. Os resultados evidenciam que os tipos de própolis brasileiras não se restringem a doze, como proposto anteriormente. As análises químicas revelaram três tipos adicionais: Maceió, Pirenópolis / Picos e Ponta Grossa / Pariquera-Açu / Mira Bela. A enorme diversidade da composição da própolis produzida no Brasil realça a importância da realização de estudos para a determinação de perfis químicos e fontes botânicas de resinas. Esses conhecimentos são essenciais para o uso adequado de produtos da própolis no mercado nacional e internacional. / Propolis is a resinous substance comprising exsudates collected from plants and substances produced by bees, with texture and colour varying according to the plant source of resin and respective phenology. This product is used in the hive with various purposes: to seal holes and line the hive entrance and to embalm the bodies of killed invaders. The interest in propolis has increased recently, mainly due to experimental evidences of its biological activities, such as cytotoxic, anti-herpes, anti-HIV, antitumoral, anti-microbial and antioxidant. The chemical composition of propolis is complex, including, in addition to beeswax, flavonoids, phenolic acids, terpenoids and volatile substances, among other constituents. The composition depends on many factors, mainly the region, where it was produced. In the present work the chemical profile of the Brazilian propolis was established based on the content of total phenolic substances, total flavonoids and waxes of samples from distinct regions of the Brazilian territory: Ponta Grossa (PR), Bauru and Pariquera-Açu (SP), Lavras and Mira Bela (MG), Pirenópolis (GO), Cabo Verde (BA), Maceio (AL) and Picos (PI). The contents of total phenols were obtained by the Folin-Ciocalteau method, using p-coumaric acid as reference. Determination of total flavonoids was based on two spectrophotometric complementary methods: alluminum chloride and dinitrophenyl-hydrazine, using quercetin and pinocembrin, respectively, as references. Determination of wax contents was carried out by extraction with chloroform, treatment with methanol and weight of the residue. The results revealed a wide chemical variety among the samples, even between samples from the same state, as are the cases of samples from Lavras and Mira Bela and from Bauru and Pariquera-Açu. Total phenol contents varied in the range 0,91%-41,63%, highest figures corresponding to red propolis from Maceio. The contents determined are higher than those obtained with propolis from Uruguai, Argentina, Paraguai, China and Europe, and also with Brazilian green propolis. Regarding values of total flavonoids, they ranged from 0,31% to 4,43%, similar to results reported by other researchers with Brazilian propolis, but lower than contents of European propolis, which has varied in the range 1,1%-22,3%. Wax contents varied from 5,37% to 45,88%, such figures being higher than values of Brazilian propolis reported by other authors, but comparable with Chinese propolis, which content is close to 30%. Based on the results obtained a Principal Components Analysis (PCA) was carried out. Samples from Maceio, Cabo Verde, Pirenópolis and Bauru emerged isolated. Pariquera-Açu and Mira Bela standed out as a group in the other end of the graphic, due to low contents of phenolic compounds and high levels of waxes. The samples from Picos, Lavras and Ponta Grossa comprised another group, based on salient contents of total phenols and relatively high contents of waxes. Chloroform and methanolic fractions from each sample were analyzed by HPLC-MS and GC-MS. These analyses showed that samples from Bauru, Lavras and Cabo Verde have composition typical of green propolis, with many prenylated phenylpropanoids and cafeoylquinic acid derivatives. The composition of the Maceio propolis differed very much, standing out by having exclusive constituents, such as chalcones, a class of flavonoids never reported for propolis. Propolis from Pirenopolis and Picos are alike due to many glycosilated flavonoids, substances also never reported for propolis. Samples from Ponta Grossa, Pariquera-Açu and Mira Bela have chemical profiles intermediate between green propolis and those with glycosilated flavonoids. The commented chemical affinities were evident in clustering analysis carried out with the identified substances as variables and UPGMA method. These results constitute evidence that Brazilian propolis cannot be grouped in only twelve types, as has been suggested. The present chemical analyses revealed three additional types: Maceió, Pirenópolis/Picos e Ponta Grossa/Pariquera-Açu/Mira Bela. The huge diversity of the composition of propolis produced in Brazil highlight the importance of studies for determination of chemical profiles and resin botanical sources. Such findings are essential for adequate use of propolis products both in the national and international market.

Following the discovery of electronic conductivity in doped polyacetylene, various studies on conducting polymers have been investigated. These polymers are essentially characterized by the presence of conjugated bonding on polymer backbone, which facilitates formation of polarons and bipolarons as charge carriers. Poly(3,4-ethylenedioxythiophene) (PEDOT) is an interesting polymer because of high electronic conductivity, ease of synthesis and high chemical stability. Electrochemically prepared PEDOT is more interesting than the polymer prepared by chemical routes because it adheres to the electrodes surface and the PEDOT coated electrodes can directly be used for various applications such as batteries, supercapacitor, sensors, etc. A majority of the studies described in the thesis are based on PEDOT. Studies on polyanthanilic acid and reduction of hydrogen peroxide on stainless steel substrate are also included. Chapter 1 provides an introduction to conducting polymers with a focus on synthesis, electrochemical characterization and applications of PEDOT. In Chapter 2, microscopic and impedance spectroscopic characterization of PEDOT coated on stainless steel (SS) and indium tin oxide (ITO) coated glass substrates are described. Electrosynthesis of PEDOT is carried out on SS electrodes by three different techniques, namely, potentiostatic, galvanostatic and potentiodynamic techniques. The SEM images of PEDOT prepared by the galvanostatatic and potentiostatic routes indicate globular morphology. However, it is seen that porosity increases by increasing the current or the potential. In the cases of both galvanostatic and potentiostatic routes, the oxidation of EDOT to form PEDOT takes place continuously during preparation. However, in the case of potentiodynamic experiment between 0 and 0.9 V vs. SCE (saturated calomel electrode), the formation of PEDOT occurs only when the potential is greater than 0.70 V. During multicycle preparation to grow thicker films of PEDOT, formation of PEDOT takes place layer by layer, a layer of PEDOT being formed in each potential cycle. PEDOT prepared in the potential ranges 0-0.90 V and 0-1.0 V show globular morphology similar to the morphology of the galvanostatically and potentiostatically prepared polymer. If prepared in the potential ranges 0-1.1 V and 0-1.2 V, the PEDOT films have rod-like and fibrous morphology. This is attributed to larger amount of PEDOT formed in each cycle in comparison with lower potential ranges and also to partial oxidation of PEDOT at potentials ≥ 1.10 V. PEDOT is also electrochemically prepared on ITO coated glass substrate. Preparation is carried out under potentiostatic conditions in the potential range between 0.9 and 1.2 V. Atomic force microscopy (AFM) studies indicate a globular topography for PEDOT films prepared on ITO coated glass plates. The height and width of globules increase with an increase in deposition potential. The PEDOT coated SS electrodes are subjected to electrochemical impedance spectroscopy studies in 0.1 M H2SO4. The Nyquist plot of impedance consists of a depressed semicircle, which arises due to a parallel combination of the polymer resistance and double-layer capacitance (Cdl). Impedance data are analyzed. Studies on electrooxidation of methanol, formic acid, formaldehyde and ethanol on nanocluster of Pt and Pt-Ru deposited on PEDOT/C electrode are reported in Chapter 3. Studies on electrooxidation of small molecules are important in view of their promising applications in fuel cells. Films of PEDOT are electrochemically deposited on carbon paper. Nanoclusters of Pt and bimetallic Pt-Ru catalysts are potentiostatically deposited on PEDOT/C electrodes. Catalysts are also prepared on bare carbon paper for studying the effect of PEDOT. The presence of PEDOT film on carbon paper allows the formation of uniform, well dispersed nanoclusters of Pt as well as Pt-Ru catalysts. TEM studies suggest that the nanoclusters of about 50 nm consist of nanoparticles of about 5 nm in diameter. Electrooxidation of methanol, formic acid, formaldehyde and ethanol are studied on Pt-PEDOT/C and PtRu-PEDOT/C electrodes by cyclic voltammetry and chronoamperometry. The data for oxidation of these small organic molecules reveal that PEDOT imparts a greater catalytic activity for the Pt and Pt-Ru catalysts. Results of these studies are described in Chapter 3. In Chapter 4, PEDOT is coated on SS substrate to investigate phenol oxidation. Studies on electrochemical oxidation of phenol are interesting because it is important to remove phenol from contaminated water or industrial effluents. Deactivation of the anode due to the formation and adsorption of polyoxyphenylene on its surface is a common problem for a variety of electrode materials, during phenol oxidation. Investigations on suitable anode materials, which can undergo no or moderate poisoning by polyoxyphenylene, are interesting. In the present study, it is shown that the electrooxidation rate of phenol is greater on PEDOT/SS electrodes than on Pt. Deactivation of PEDOT/SS electrode is slower in relation to Pt. The oxidation of phenol on PEDOT/SS electrode occurs to form both polyoxyphenylene and benzoquinone in parallel. Cyclic voltammetry of phenol oxidation is studied by varying the concentration of phenol, sweep rate and thickness of PEDOT. Ac impedance studies indicate a gradual increase in polymer resistance due to adsorption of polyoxyphenylene during multi sweep cyclic voltammetry. This investigation reveals that PEDOT coated on a common metal or alloy such as SS is useful for studying electrooxidation of phenol, which is generally studied on a noble metal based electrodes. Electrochemically prepared PEDOT is used for supercapacitor studies and the results are presented in Chapter 5. Generally, electronically conducting polymers possess high capacitive properties due to pseudo-faradaic reactions. PEDOT/SS electrodes prepared in 0.1 M H2SO4 are found to yield higher specific capacitance (SC) than the electrodes prepared from neutral aqueous electrolyte. The effects of concentration of H2SO4, concentration of SDS, potential of deposition and nature of supporting electrolytes used for capacitor studies on SC of the PEDOT/SS electrodes are studied. Specific capacitance values as high as 250 F g-1 in 1 M oxalic acid are obtained during the initial stages of cycling. However, there is a decrease in SC on repeated charge-discharge cycling. Spectroscopic data reflect structural changes in PEDOT on extended cycling. Self-doped PANI is expected to possess superior electrochemical characteristics in relation to PANI. The self-doping is due to the presence of an acidic group on the polymer chain. However, self-doped PANI is soluble in acidic solutions against insolubility of PANI. In the present study, poly(anthranilic acid), PANA, is encapsulated in porous Nafion membrane by chemical and a novel electrochemical methods. PANA present in solid form in Nafion membrane does not undergo dissolution in acidic solutions. The methods of preparation and various electrochemical, optical and spectroscopic characterizations studies of PANA-Nafion are described in Chapter 6. Electroreduction of H2O2 is studied on sand-blasted stainless steel (SSS) electrode in an aqueous solution of NaClO4 and the details are reported in Chapter 7. The cyclic voltammetric reduction of H2O2 at low concentrations is characterized by a cathodic peak at -0.40 V versus standard calomel electrode (SCE). Cyclic voltammetry is studied by varying the concentration of H2O2 in the range from 0.2 mM to 20 mM and the sweep rate in the range from 2 to 100 mV s-1. Cyclic voltammograms at concentrations of H2O2 higher than 2 mM or at high sweep rates consist of an additional current peak, which may be due to the reduction of adsorbed species formed during the reduction of H2O2. Amperometric determination of H2O2 at -0.50 V vs. SCE provides the detection limit of 5 μM H2O2. A plot of current density versus concentration has two linear segments suggesting a change in the mechanism of H2O2 reduction at concentrations of H2O2 ≥ 2 mM. From the rotating disc electrode study, diffusion co-efficient of H2O2 and rate constant for reduction of H2O2 are evaluated. Thus, stainless steel, which is inexpensive and a common alloy, is useful for studying electrochemical reduction of H2O2 and also for analytical application. This work is initiated to study the reduction of H2O2 on PEDOT/SS electrodes. As a result of preliminary experiments, it is found that PEDOT does not exhibit any influence on the kinetics of H2O2 reduction. Therefore studies conducted using bare stainless steel are included in this chapter. Results of the above studies are described in the thesis.

In this study, extracts from bark, leaves and catkins of Salix aegyptiaca L. were investigated for their antioxidant content by 2,2-diphenyl-2-picrylhydrazyl hydrate (DPPH) free radical quenching assay, total phenolic and total flavonoid assays. The highest antioxidant activity (19 ug/ml IC50 for inhibition of DPPH radical activity), total phenolic content (212 mg gallic acid equivalents/g of dried extract) and total flavonoid (479 mg catechin equivalents/g of dried extract) was observed in the ethanolic extract of bark. High performance liquid chromatography (HPLC) analyses revealed the presence of gallic acid, caffeic acid, vanillin and p-coumaric acid, myricetin, catechin, epigallocatechin gallate, rutin, quercetin as well as salicin. In addition, the anti-proliferative effects of the ethanolic extracts on colorectal cancer cell lines (HCT-116 and HT-29) were examined by an MTT cell viability assay while their apoptotic effects were assayed by acridine orange staining and caspase 3 activity. The results indicate that the ethanolic extract of bark of S. aegyptiaca can strongly inhibit cell proliferation and induces apoptosis in a dose dependent manner on both cell lines. We propose that extracts from this plant may be utilized as a source of health promoting antioxidants. Our data provide a perspective for more detailed study of biochemical pathways associated with the cancer preventive effects of active components of the extracts from S. aegyptiaca.

No description available.

A novel non-destructive method of grape berry analysis is presented that uses reflected light to predict berry composition. The reflectance spectrum was collected using a diode array spectrometer (350 to 850 nm) over the 2009 and 2010 growing seasons. Partial least squares regression (PLS) and support vector machine regression (SVMR) generated calibrations between reflected light and composition for five berry components, total soluble solids (°Brix), titratable acidity (TA), pH, total phenols, and anthocyanins. Standard methods of analysis for the components were employed and characterized for error. Decomposition of the reflectance data was performed by principal component analysis (PCA) and independent component analysis (ICA). Regression models were constructed using 10x10 fold cross validated PLS and SVM models subject to smoothing, differentiation, and normalization pretreatments. All generated models were validated on the alternate season using two model selection strategies: minimum root mean squared error of prediction (RMSEP), and the "oneSE" heuristic. PCA/ICA decomposition demonstrated consistent features in the long VIS wavelengths and NIR region. The features are consistent across seasons. 2009 was generally more variable, possibly due to cold weather affects. RMSEP and R2 statistics of models indicate that PLS °Brix, pH, and TA models are well predicted for 2009 and 2010. SVM was marginally better. The R2 values of the PLS °Brix, pH, and TA models for 2009 and 2010 respectively were: 0.84, 0.58, 0.56 and: 0.89, 0.81, 0.58. 2010 °Brix models were suitable for rough screening. Optimal pretreatments were SG smoothing and relative normalization. Anthocyanins were well predicted in 2009, R2 0.65, but not in 2010, R2 0.15. Phenols were not well predicted in either year, R2 0.15-0.25. Validation demonstrated that °Brix, pH, and TA models from 2009 transferred to 2010 with fair results, R2 0.70, 0.72, 0.31. Models generated using 2010 reflectance data did not generate models that could predict 2009 data. It is hypothesized that weather events present in 2009 and not in 2010 allowed for a forward calibration transfer, and prevented the reverse calibration transfer. Heuristic selection was superior to minimum RMSEP for transfer, indicating some overfitting in the minimum RMSEP models. The results are demonstrative of a reflectance-composition relationship in the VIS-NIR region for °Brix, pH, and TA requiring additional study and development of further calibrations.

High Arctic permafrosted soils represent a massive sink in the global carbon cycle, accounting for twice as much carbon as what is currently stored as carbon dioxide in the atmosphere. However, with current warming trends this sink is in danger of thawing and potentially releasing large amounts of carbon as both carbon dioxide and methane into the atmosphere. It is difficult to make predictions about the future of this sink without knowing how it has reacted to past temperature and climate changes. This dissertation summarizes the results of the first study to look at long term, fine scale organic carbon delivery by the high-Arctic Colville River into Simpson’s Lagoon in the near-shore Beaufort Sea. Modern delivery of organic carbon to the Lagoon was determined to come from a variety of sources through the use of a three end-member mixing model and sediment biomarker concentrations. These sources include the Colville River in the western area of the Lagoon near the river mouth, marine sources in areas of the Lagoon without protective barrier islands, and coastal erosional sources and the Mackenzie River in the eastern area of the Lagoon. Downcore organic carbon delivery was measured on two cores in the Lagoon, one taken near the mouth of the Colville River (spans about 1800 years of history) and one taken on the eastern end of the Lagoon (spans about 600 years of history). Bulk organic parameters and biomarkers were measured in both cores and analyzed with Principle Component Analysis to determine long-term trends in organic carbon delivery. It was shown that at various times in the past, highly degraded organic carbon inputs of what is likely soil and peat carbon were delivered to the Lagoon. At other times, inputs of fresher, non-degraded, terrestrially-derived organic carbon inputs of what are likely higher amounts of plant and vegetative material was delivered to the Lagoon. Inputs of degraded soil carbon were also shown to correspond to higher temperatures on the North Slope of Alaska, likely indicating that warmer temperatures lead to a thawing of permafrost and in turn organic carbon mobilization to the coastal Beaufort Sea.

Thesis (M. Sc.Voedselwet.)--University of Stellenbosch, 2001. / ENGLISH ABSTRACT: Phenolic compounds in wine, due to their antioxidant activity, are reportedly responsible for the health-promoting properties of wines. The effect of cultivar and in-bottle ageing on the antioxidant activity of South African wines in different types of antioxidant assays was, therefore, investigated. The antioxidant activity of commercial South African red (Cabernet Sauvignon, Ruby Cabernet, Pinotage, Shiraz, Merlot) and white (Sauvignon blanc, Chenin blanc, Chardonnay, Colombard) cultivar wines was compared using the 2,2’-azino-di-(3-ethylbenzothialozine-sulphonic acid) radical cation (ABTS·+) scavenging, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH·) scavenging and microsomal lipid peroxidation (MLP) assays. The red wines was more effective than the white wines on an “as-is” and an equal total phenol content. The total antioxidant activity (TAAABTS and TAADPPH) of Ruby Cabernet was the lowest of the red wines, but the antioxidant potency (APABTS and APDPPH) of red wine phenolic fractions did not differ (P ³ 0.05). Ruby Cabernet and Pinotage were the least effective inhibitors of MLP, while Merlot was the most effective of the red wines. Pinotage phenolic fractions had lower (P < 0.05) APMLP than that of other red wines. Of the white wines, Chardonnay and Chenin blanc had the highest and lowest effectivity respectively according to all antioxidant parameters. Ascorbic acid present in some wines increased and decreased their TAA and % MLP inhibition respectively. TAA and % MLP inhibition correlated well (r ³ 0.7, P < 0.001) with total phenol content of red and white wines, as well as with flavanol content of red wines and tartaric acid ester content of white wines. The % MLP inhibition also correlated well with flavanol content of white wines. No correlation (P > 0.01) was obtained between TAA or % MLP inhibition and monomeric anthocyanin content of red wines. In the deoxyribose assay, red wines were more pro-oxidant and exhibited lower hydroxyl radical scavenging and metal chelating abilities than white wines. The effect of in-bottle ageing on antioxidant activity of wines was determined using the ABTS·+ and DPPH· scavenging assays. The TAA and total phenol content of experimental red (Pinotage and Cabernet Sauvignon)and white (Chardonnay and Chenin blanc) cultivar wines, decreased (P < 0.05) during 12 months of storage at 0, 15 and 30 ºC. The TAAABTS of Cabernet Sauvignon and Chardonnay, stored at 30 ºC were lower (P < 0.05) than at 0 ºC. The APABTS and APDPPH of most wines also decreased during storage. The monomeric anthocyanin content of red wines decreased (P < 0.05) rapidly at 15 and 30 ºC. The flavanol content of wines (except Chenin blanc) increased during the first 9 months, decreasing again after 12 months, while minor changes in the flavonol and tartaric acid ester content of both red and white wines were observed. The TAAABTS exhibited a good correlation (r ³ 0.7, P < 0.001) with total phenol content of red and white wines, as well as with flavonol and tartaric acid ester content of red and white wines and flavanol content of white wines. The monomeric anthocyanin content of red wines correlated (r = 0.50, P < 0.001) weakly with TAAABTS. The decrease in the TAAABTS of wines could thus be mainly attributed to a decrease in their total phenol content. / AFRIKAANSE OPSOMMING: Die antioksidant aktiwiteit van fenoliese komponente in wyn is waarskynlik verantwoordelik vir die gesondheidsvoordele daarvan. Die studie het dus gepoog om effek van kultivar en veroudering na bottelering op die antioksidant aktiwiteit van Suid-Afrikaanse wyne te ondersoek. Die antioksidant aktiwiteit van kommersiële Suid-Afrikaanse rooi (Cabernet Sauvignon, Ruby Cabernet, Pinotage, Shiraz, Merlot) en wit (Sauvignon blanc, Chenin blanc, Chardonnay, Colombard) kultivarwyne is vergelyk deur middel van die 2,2’-azino-di-(3-etielbensotialosien-sulfoon suur)-radikaal katioon (ABTS·+) vernietigingstoets, 2,2-difeniel-1-pikrielhidrasielradikaal (DPPH·) vernietigingstoets en mikrosomale lipiedperoksidasietoets (MLP). Die antioksidant aktiwiteit en die antioksidant kragtigheid (AK) van die rooiwyne was beter as dié van witwyne in al drie antioksidant toetse. Die totale antioksidant aktiwiteit (TAAABTS en TAADPPH) van Ruby Cabernet was die laagste van die rooiwyne, terwyl die AKABTS en AKDPPH van rooiwyn fenoliese fraksies nie van mekaar verskil (P ³ 0.05) het nie. Van die rooiwyne, het Ruby Cabernet en Pinotage die laagste en Merlot die hoogste effektiwiteit in die MLP toets getoon. Die AKMLP van Pinotage se fenoliese fraksies was die laagste van die rooiwyne. Die witwyne, Chardonnay en Chenin blanc, het onderskeidelik die beste en swakste antioksidant aktiwiteit en AK van die witwyne getoon in al drie antioksidant toetse. Askorbiensuur wat in sommige witwyne voorgekom het, het die TAA van hierdie wyne verhoog, maar hul % MLP inhibisie verlaag. Die TAA en % MLP inhibisie het goed gekorreleer (r ³ 0.7, P < 0.001) met die totale fenolinhoud van rooi- en witwyne, asook die flavanolinhoud van rooiwyne en die wynsteensuur-esterinhoud van witwyne. Die % MLP inhibisie het ook goed gekorreleer met die flavanolinhoud van witwyne. Geen korrelasie (P > 0.1) is waargeneem tussen antioksidant aktiwiteit van rooiwyne en hul monomeriese antosianien-inhoud. Rooiwyn was meer pro-oksidatief in die deoksieribose toets as witwyne, maar was die swakste hidroksieradikaalvernietigers en metaalcheleerders.Die effek van veroudering na bottelering op die antioksidant aktiwiteit van wyne soos bepaal met die ABTS·+ en DPPH· vernietigingstoetse, is ondersoek. Die TAA en die totale fenolinhoud van eksperimentele rooi- (Pinotage en Cabernet Sauvignon) en witwyne (Chardonnay en Chenin blanc) het afgeneem (P < 0.05) tydens opberging na bottelering by 0, 15 en 30 ºC oor 12 maande. Opberging by 30 ºC het ‘n groter vermindering (P < 0.05) in die TAAABTS waarde vir Cabernet Sauvignon en Chardonnay veroorsaak as by 0 ºC. Die meeste wyne se APABTS en APDPPH waardes het ook verminder (P < 0.05) na 12 maande. Drastiese vermindering (P < 0.05) in die monomeriese antosianieninhoud van rooiwyne is opgemerk tydens opberging by 15 en 30 ºC. Tydens die eerste 9 maande se opberging het die flavanolinhoud van wyne toegeneem (P < 0.05) en daarna afgeneem (P < 0.05) tot by 12 maande, terwyl flavonol- en wynsteensuuresterinhoud van beide rooi- en witwyne min verandering ondergaan het. Die totale fenolinhoud van rooi- en witwyne, asook die flavonol en wynsteensuur-esterinhoud van rooi-en witwyne en die flavanolinhoud van witwyne, het goed gekorreleer (r ³ 0.7, P < 0.001) met die TAAABTS. In teenstelling met die resultate vir kommersiële kultivarwyne, was die TAAABTS van rooiwyne swak gekorreleer (r = 0.5, P < 0.001) met hul monomeriese antosianieninhoud. Die afname in TAAABTS van wyne tydens veroudering kon dus meestal toegeskryf word aan die afname in hul totale fenolinhoud.

Thesis (MScFoodSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The phenolic composition of Cyclopia species is believed to be partially responsible for the numerous health promoting properties associated with their extracts. Current quality control measures do not accommodate variation in phenolic profiles of Cyclopia species. In this study, comprehensive high performance liquid chromatography (HPLC) methods were developed for the improved characterisation of the phenolic composition of aqueous extracts of two Cyclopia species (C. subternata and C. maculata). The methods were developed to be suitable for both routine quantitative analysis on conventional HPLC instrumentation, and the construction of chromatographic fingerprints for further data analysis. The latter entailed similarity analysis and prediction of total antioxidant capacity (TAC). Using a methodical approach, two separate HPLC methods, using diode array detection (DAD), were developed and validated for the analysis of aqueous extracts prepared from unfermented (green) and fermented plant material of C. subternata and C. maculata. Separation was achieved using the same method parameters (column, temperature, mobile phases), except for differing mobile phase gradients. Hyphenation of the developed HPLC methods with mass spectrometry (MS) and tandem MS allowed the confirmation of phenolic compounds previously identified in Cyclopia, and the tentative identification of several additional compounds in Cyclopia species, which are reported here for the first time. These included apigenin-6,8-di- C-glucoside, 3-hydroxyphloretin-30,50-di-C-hexoside, eriodictyol-di-C-glucoside, iriflophenone-di-O,C-hexoside, hydroxymangiferin and hydroxyisomangiferin. Subsequently, a large number of aqueous extracts of randomly selected green C. subternata (n = 64) and C. maculata (n = 50) plant material samples were analysed. Large quantitative variations were observed on intra- and inter-species levels. Cyclopia maculata extracts contained almost six times more mangiferin than extracts from C. subternata. HPLC-DAD analysis produced duplicate fingerprints for each extract which were consequently used for further analysis. The chromatographic fingerprint of a bioactive extract of each species was included in the respective data sets. Similarity analysis was conducted between the fingerprints from the randomly selected extracts and the corresponding active extract. For each species several extracts were determined to have similar “activity” as that of the active extract (n = 15 for C. subternata and n = 45 for C. maculata). Compounds potentially responsible for the activity were tentatively identified with the aid of principal component analysis (PCA) in combination with similarity analysis. PCA was more effective in identifying small differences between fingerprints than similarity analysis based on the correlation coefficients (r) alone. Furthermore, multivariate data analysis was used to construct partial least squares (PLS) regression models for the prediction of TAC from fingerprint data of each species, and available data from two microplate TAC assays. The construction of the models was successful with reasonable errors (< 10%), and permitted the determination of compounds of interest for future research. These included compounds of known identity that had large positive contributions toward the predictions of TAC, or unknown compounds that had small UV signals, but relatively large positive contributions to the models. / AFRIKAANSE OPSOMMING: Die talle gesondheidbevorderingseienskappe van ekstrakte van Cyclopia spesies word gedeeltelik geassosieer met hul fenoliese samestelling. Huidige kwaliteitskontrolemaatreëls is nie in staat om die variasie wat in die fenoliese profiele van die spesies voorkom, te akkommodeer nie. Omvattende hoë druk vloeistof chromatografiese (HPLC) metodes is vir twee Cyclopia spesies, naamlik C. subternata en C. maculata, in hierdie studie ontwikkel vir beter karakterisering van die fenoliese samestelling van waterekstrakte van dié spesies. Die metodes moes ook geskik wees vir roetine analise van C. subternata en C. maculata ekstrakte op konvensionele HPLC instrumentasie, en vir die opstel van chromatografiese vingerafdrukke (fenoliese samestellingsprofiele) vir verdere data analise, soos gelykvormigheidsanalise en die voorspelling van die totale antioksidantkapasiteit (TAC). Twee HPLC metodes, wat van ’n ultraviolet-diode detektor (DAD) gebruik maak, is ontwikkel deur ’n sistematiese benadering te volg. Die onderskeie metodes is vir die ontleding van waterekstrakte van groen (ongefermenteerde) en gefermenteerde plantmateriaal van C. subternata en C. maculata gevalideer. Ongeag die spesie is optimale skeiding met dieselfde kolom, mobiele fase en kolom-temperatuur bereik, maar met verskillende mobiele fase gradiënte. Analise met massaspektrometrie (MS) en tandem MS het die teenwoordigheid van fenoliese verbindings, wat voorheen in Cyclopia spesies geidentifiseer is, bevestig. Verder is ook ’n aantal verbindings vir die eerste keer in Cyclopia tentatief geidentifiseer. Dit sluit apigenien-6,8-di-C-glukosied, 3- hidroksiefloretien-30,50-di-C-heksosied, eriodiktiol-di-C-glukosied, iriflofenoon-di-O,C-heksosied, hidroksiemangiferien en hidroksie-isomangiferien in. Vervolgens is ’n groot aantal ewekansig gekose waterekstrakte van beide groen C. subternata (n = 64) en C. maculata (n = 50) plantmateriaal geanaliseer, en groot kwantitatiewe variasie op intra- en inter-spesievlak waargeneem. Cyclopia maculata ekstrakte het byvoorbeeld byna ses maal die mangiferieninhoud van C. subternata ekstrakte gehad. HPLC-DAD analise van die ekstrakte het duplikaat vingerafdrukke van elke ekstrak geproduseer, wat vir verdere data analise gebruik is. Die chromatografiese vingerafdruk van ’n bioaktiewe ekstrak van elke spesie was by die onderskeie datastelle ingesluit. Gelykvormigheidsanalise is tussen vingerafdrukke van die ewekansig gekose ekstrakte en die ooreenstemmende aktiewe ekstrak uitgevoer. Vir elke spesie is ’n aantal “aktiewe” ekstrakte aangewys (n = 15 vir C. subternata en n = 45 vir C. maculata). Die verbindings wat potensieel verantwoordelik kan wees vir die aktiwiteite is met behulp van hoofkomponentontleding (PCA) in kombinasie met gelykvormigheidsanalise, tentatief aangewys. PCA was egter meer effektief om klein verskille tussen vingerafdrukke aan te dui, in vergelyking met gelykvormigheidsanalise wat slegs op die korrelasie koëffisiënt (r) gebaseer is. Meerveranderlike data analiese is gebruik om “gedeeltelike kleinste kwadrate” (PLS) regressiemodelle, vir die voorspelling van die TAC van beide spesies te bou. Die voorspelling is gebaseer op hul vingerafdruk data en TAC data van twee TAC mikroplaat metodes. Die model-konstruksie was suksesvol met aanvaarbare voorspellingsfoute (< 10%). Verbindings van belang kon ook bepaal word. Dit sluit bekende verbindings in wat groot positiewe bydraes ten opsigte van die voorspelling van TAC getoon het, asook ongeidentifiseerde verbindings wat klein UV-seine getoon het, maar relatiewe groot bydraes tot die modelle gehad het.