A antracnose da videira tem como agente causal o fungo Elsinoë ampelina Shear, o qual ataca tecidos tenros da parte aérea causando lesões necróticas e comprometendo o desenvolvimento da planta com consequente queda na quantidade e qualidade dos frutos produzidos. Cultivares de Vitis apresentam diferentes níveis de susceptibilidade à antracnose. Uma vez que características anatômicas e químicas podem atuar como mecanismos de resistência a patógenos, o presente estudo propõe comparar caracteres histológicos e bioquímicos em folhas jovens de Vitis labrusca \'Niagara Rosada\' (NR, susceptível), Vitis vinifera \'Thompson Seedless\' (TS, susceptível) e V. vinifera \'Pinot Noir\' (PN, resistente). As análises anatômicas foram realizadas em folhas sadias aos 4 e 11 dias após o brotamento (DAB) e em folhas lesionadas com 11 DAB, enquanto os compostos bioquímicos foram quantificados em folhas sadias aos 4 e 11 DAB. Os caracteres analisados foram: índice estomático, densidade de idioblastos cristalíferos, espessura da cutícula da face adaxial, espessura da parede periclinal externa e altura das células epidérmicas de ambas as faces, espessura do mesofilo total, do parênquima paliçádico e do parênquima lacunoso, o conteúdo de compostos fenólicos totais, flavonoides e de clorofila a, b e total, bem como a atividade de peroxidase e de polifenoloxidase. Os dados obtidos foram submetidos à análise estatística. A cultivar TS apresentou índice estomático maior nas duas idades avaliadas em comparação com o genótipo resistente PN, a qual apresentou maior espessura de cutícula nas duas idades e de mesofilo total aos 11 DAB. Os parâmetros quantitativos das amostras inoculadas apresentaram redução significativa em relação às não inoculadas, com exceção da área foliar de PN, a qual não foi significativamente menor. Para NR e TS, 100% das amostras inoculadas apresentaram várias lesões expandidas, enquanto PN apenas 60% das folhas analisadas apresentaram poucas lesões bem delimitadas e de formato circular. A cultivar resistente PN apresentou forte reação positiva a compostos fenólicos bem como o maior conteúdo desses compostos na idade 11 DAB, enquanto a cultivar susceptível TS apresentou reação muito fraca e a menor concentração. O conteúdo de flavonoides foi maior em PN em relação à TS nas duas idades avaliadas, e NR apresentou o valor mais baixo aos 4 DAB, quando é altamente susceptível. A atividade de polifenoloxidase aos 11 DAB foi maior na cultivar PN, intermediária em NR e mais baixa em TS. A análise de todos os parâmetros anatômicos e bioquímicos avaliados indica que a maior resistência da cultivar PN esteja relacionada ao menor índice estomático, à cutícula mais espessa, ao conteúdo mais elevado de compostos fenólicos totais e de flavonoides, bem como a maior atividade enzimática de polifenoloxidase. / Grapevine anthracnose is caused by the fungus Elsinoë ampelina Shear, which attacks tissues of the aerial part causing necrotic lesions, compromising plant growth with consequent decrease in quantity and quality of the fruits produced. Vitis cultivars show different levels of susceptibility to anthracnose. Anatomical and genetic characteristics can act as a resistance mechanism against pathogens, therefore, this study proposes to compare histological and biochemical characteristics in young leaves of Vitis labrusca \'Niagara Rosada\' (NR, susceptible), Vitis vinifera \'Thompson Seedless\' (TS, susceptible) and V. vinifera \'Pinot Noir\' (PN, resistant). The anatomical analyses were performed on healthy leaves at 4 and 11 days after budding (DAB) and at 11 DAB on lesioned leaves, while biochemical compounds were quantified on healthy leaves at 4 and 11 DAB. The features analyzed were: stomatal index, idioblasts density, adaxial face cuticle thickness, external periclinal wall thickness, epidermal cell height of both faces, total mesophyll thickness, palisade parenchyma and spongy parenchyma, total phenolic compounds content, flavonoids, chlorophyll a, b, and total, and peroxidase and polyphenoloxidase activity. The data were submitted to the statistical analysis. The TS cultivar had a higher stomatal index at both ages evaluated compared to the PN resistant genotype, which presented greater cuticle thickness at leaf ages and total mesophyll at 11 DAB. The quantitative parameters of the inoculated samples presented a significant reduction in relation to the non- inoculated, except for the PN leaf area, which was not significantly lower. For NR and TS, 100% of the inoculated samples presented several expanded lesions, whereas PN only 60% of the analyzed leaves showed few lesions well delimited and circular in shape. The resistant cultivar PN showed strong positive reaction to phenolic compounds as well as the highest content of these compounds at 11 DAB, while the TS susceptible cultivar presented very weak reaction and the lowest concentration. The content of flavonoids was higher in PN compared to TS at both ages evaluated, and NR presented the lowest flavonoid content at 4 DAB, when it was highly susceptible. The polyphenoloxidase activity at 11 DAB was higher in the PN cultivar, intermediate in NR, and lower in TS. The analyses of all the anatomical and biochemical parameters indicate that the higher resistance of the PN cultivar is related to the lower stomatal index, thicker cuticle, higher content of total phenolic compounds and flavonoids, as well as higher enzymatic activity of polyphenoloxidase.

Potato peel, a waste generated from potato processing is a disposal problem. But, it is a good source of phenolic compounds, sugars, and glycoalkaloids. This study examines the subcritical water extraction of phenolics, glycoalkaloids and sugars from potato peel and compares it to conventional solvent extraction. Experiments were conducted in a batch stainless steel reactor at 6 MPa, 2 mL/min and 100 to 240C for 30-120 min. The results revealed that highest recoveries of phenolic compounds (81.23 mg/100 g; fw) and sugars (75 mg/g; fw) were obtained using subcritical water at 180C and 30 min and at 160C and 120 min, respectively. Low content of glycoalkaloids (1.19 mg/100 g, fw) was obtained using subcritical water. The yields of phenolics and sugars using subcritical water were 40 and 45% higher than using a conventional solvent extraction method. Therefore, subcritical water might be a good substitute to organic solvents such as methanol and ethanol to obtain functional ingredients from potato peel. / Food Science and Technology

The main objective of the study was to encapsulate the phenolic compounds from sour cherry pulp in micro size, to investigate the physicochemical properties of capsules and their digestability in simulated gastric and intestinal fluid. The effect of different coating materials, ultrasonication time and core to coating ratio on encapsulation of phenolic compounds from sour cherry pomace was investigated. Maltodextrin and gum Arabic were chosen as coating materials. Coating material was prepared with different maltodextrin:gum Arabic (MD:GA) ratios of 10:0, 8:2, 6:4 to make the total solid content 10%. In addition, two different core to coating ratios of 1:10 and 1:20 were used. Emulsions were prepared by homogenization through ultrasonication at 160 W power and 20 KHz frequency for different time periods (5-30 min). Then, the emulsions were freeze dried for 48 hours to obtain the microcapsules. Encapsulation efficiency, antioxidant activity, surface morphology, particle size, color, digestability and glass transition temperatures of the microcapsules were determined. The microcapsules with a core to coating ratio of 1:20 were found to have higher encapsulation efficiencies (78.80-92.26%) than those with a core to coating ratio of 1:10 (69.38-77.83%). Increasing the gum Arabic ratio in the coating material increased encapsulation efficiency. Optimum conditions for encapsulation with the highest efficiency and the lowest particle size were sonication time of 22.5 min, MD:GA ratio of 8:2 and core to coating ratio of 1:20. Encapsulation was effective in preventing the release of the phenolic compounds in gastric fluid. On the other hand, phenolic compounds were released from the capsules into the intestinal fluid.

ABC type amphiphilic triblock copolymers, polyethylene-b-poly(ethylene oxide)-b-poly (£`-caprolactone) (PE-b-PEO-b-PCL), were synthesized through ring-opening polymerization. We have successfully synthesized hierarchical mesoporous silicas using a simple evaporation-induced self-assembly (EISA) strategy. Two blocks of hydrophobic segment (PE and PCL) in the triblock copolymer (PE-b-PEO-b-PCL) involved in two-type mesepores after calcinations. We recognized the PE segment attributed to face centered cubic (f. c. c.) morphology (spherical pore) and the PCL segment attributed to tetragonal cylinder structure (cylinder pore) by small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and specific surface area & pore size distribution analyzer (BET), respectively. We also investigated the effect on pore size and morphology with changing the molecular weight of PCL and the ratios of TEOS/template/HCl. We also synthesized the mesoporous phenolic resin by triblock copolymer poly(ethylene oxide)-b-poly(£`-caprolactone)-b-poly(L-lactide) (PEO-b-PCL-b-PLLA). After curing and calcinations, we also explored the morphology and pore size distribution of mesoporous phenolic by SAXS, TEM, BET. Because of the sequence of hydrophobic segment PCL and PLLA lay in the same side, so we could only observe hexagonal cylinder structure and one pore size.

The influence of genotype (selection), location, and year on antioxidant activity (AOA), total phenolics (TP), total carotenoids (TC), phenolic and carotenoid composition was studied using specialty (colored) potatoes (Solanum tuberosum L.) from the Texas Potato Variety Development Program, grown at two Texas locations (McCook and Dalhart), and in two years (2003 and 2004). Chlorogenic acid, gallic acid, catechin, caffeic acid, and malvidin-3-(p-coumaryl rutinoside)–5-galactoside were the major phenolics, and lutein and violaxanthin were the major carotenoids identified. The AOA, TP, and TC and phenolic composition differed significantly with genotype, location and year. However, genotypic effects were larger than location and year effects. Selection CO112F2-2 was high in all the measured parameters and also stable across locations and years, suggesting that this selection could be used as a parent in breeding varieties with improved health benefits. The AOA, TP and chlorogenic acid content were highly significantly correlated with one another. The effects of whole specialty potato extracts, fractions and individual compounds on LNCaP (androgen-dependent) and PC-3 (androgen-independent) prostate cancer cells were also investigated. Ethanol extract of the selection CO112F2-2 (5 µg chlorogenic acid eq/ml), the anthocyanin fraction (AF; 5 µg chlorogenic acid eq/ml), gallic acid and chaconine showed potent anti-proliferative properties and increased the cyclin-dependent kinase inhibitor p27 levels in LNCaP and PC-3 cells. Induction of apoptosis was cell context dependent and associated with JNK (c-Jun NH2-terminal Kinase) and Erk (extracellular signal regulated kinase) activation. Cell death pathways, induced by potato extract and the AF, were associated with Erk and JNK activation, and these kinases activated caspase-independent apoptosis through nuclear translocation of endonuclease G (endo G) and apoptosis-inducing factor (AIF) in both cell lines. Induction of caspase-dependent apoptosis was also kinase-dependent but was observed only in LNCaP cells. Kinase inhibitors reversed this nuclear translocation of endo G and AIF. This is the first report showing that the cytotoxic activities of potato extract/AF in cancer cells were due to activation of caspase-independent apoptosis.

Phenolic compounds are the chemicals which are used by many different industries and as a result of this spread to the environment. These compounds can be absorbed easily through the human and animal skin and through the mucosal membrane, mix in to the blood circulation and thus create a toxic effect on several tissue and organs including, liver, lung and kidneys. For this reason, determination of phenolic compounds emitted to environment is a very important issue. In fact, there are standard methods for the determination of these compounds like HPLC, Spectrophotometric and calorimetric methods however, these are time consuming methods and requires to be expertise. On the other hand, there are also different types of biosensors developed for the phenolic compound detection. In this study, a new, disposable, cheap and convenient tyrosinase biosensor was developed for the phenolic compound detection. By means of absorption method, the enzyme tyrosinase and the chromophore MBTH were immobilized on the support material and as a model substrate L- dopa was used. As a result of optimization studies 1mg/ml tyrosinase concentration and 1.5mM MBTH concentration were determined for using in biosensor construction. Detection limit of l-dopa, model substrate, found as 0,064 mM and for other phenolic compounds, 4-chlorophenol, catechol, m-cresol and p-cresol, detection limit was obtained 0.032 mM, 0.032 mM, 0.128 mM, 0.128 mM, respectively. In addition, we found that the biosensor response was not affected by pH changes ranging from 3 to 11. The stability of biosensor which is one of the important parameter for commercialization was not change through 70 days at room temperature and 4&deg / C when compared to at the beginning response.

The main object of the presented study was investigation of the use of cross-linked enzyme (tyrosinase) aggregates (CLTA) obtained from crude mushroom extract for a rapid phenolic content analysis in wines. In addition, a comparison of phenolic characteristics of Turkish red wines was performed. Reproducible and reliable results in total phenolic measurement were obtained with CLTAs similar to pure tyrosinase and tyrosinase obtained from crude mushroom extract. Measurement of total phenolic content is possible both in standard solutions and in complex matrices, such as wine. In a very short time period, 10 seconds, phenolics content in red and white wines produced from grapes of Turkey were investigated by using CLTAs. Results were consistent when compared to a well known phenolic measurement method, Folin-Ciocalteau. CLTAs exhibited very high operational stability and retained more than 90% of its activity after 30th use. Moreover, it showed good shelf-life stability for about 2 months storage by maintaining 90% of its maximum activity. So, use of CLTAs prepared from crude mushroom extract is an effective, fast and cheap alternative in total phenolics measurements in wines. Moreover, a novel catalase phenoloxidase (CATPO) produced by a fungal microorganism, Scytalidium thermophilum, was studied to check its capabilities in phenolics measurements. This novel catalase phenol oxidase showed similarly good results, exhibiting widesubstrate selectivity.

The objective of this study was to compare microwave assisted extraction (MAE) and conventional extraction methods for the extraction of total phenolic compounds (TPC) from tomato and sour cherry pomace. Antiradical efficiency (AE) of the extracts and also the concentration of phenolic compounds were determined. In MAE, the effects of microwave power (400 and 700 W), solvent type (water, ethanol and ethanol-water mixture at 1:1 v/v), extraction time (8-20 min) and solvent to solid ratio (10, 20 and 30 ml/g) were studied to observe the change of TPC and AE of the extracts. Conventional extraction was conducted for 6 h using different solvent to solid ratios (10, 20 and 30 ml/g) and solvent types (water, ethanol and ethanol-water mixture at 1:1 v/v). When the power increased from 400 W to 700 W, TPC and AE values increased. In MAE, maximum TPC and AE values were obtained at a solvent to solid ratio of 20 ml/g. The highest TPC and AE values were obtained when the ethanol-water mixture was used for both MAE and conventional extraction. The highest TPC and AE of tomato pomace extracts was determined as 3.76 mg gallic acid equivalent, GAE/g sample and 4.84 mg 1,1-diphenyl-2-picrylhydrazyl, DPPH/g sample, respectively in MAE using power level of 700 W, ethanol-water mixture, solvent to solid ratio of 20 ml/g and extraction time of 14 min. The major phenolic acids detected in tomato pomace extract were gentisic acid and vannilic acid. For sour cherry pomace extracts, the highest TPC and AE was found as 14.14 mg GAE/g sample and 28.32 mg DPPH/g sample, respectively in MAE using power level of 700 W, solvent to solid ratio of 20 ml/g, ethanol-water mixture and extraction time of 12 min. Epicatechin was found to be the major phenolic acid in sour cherry pomace. There was no significant difference in different extraction methods in terms of TPC. On the other hand, AE value and concentration of major phenolic acids of tomato and sour cherry pomace increased when MAE was used.

Turkey is important major licid opium poppy (Papaver Somniferum) producer for medicinal and scientific purposes in the world and one of the two traditional producer country. The poppy seeds which are unique part of the opium poppy are used for food purpose. About 25.000 ton/year poppy seeds were produced for food purpose. Recent years morphine content of commercially available poppy seeds were speculated. Some studies have been reported that poppy seeds from different origins contain a wide variation of morphine (2 &ndash / 294) &mu / g/g content. They have been used also different sample preparation method (extraction and derivatization) and different instruments (GC-MS) during analyses. In this study morphine content was determined in Turkish origin which were white, yellow and blue poppy seeds colors by using high pressure liquid chromatography (HPLC). Different sample preparation method (without derivatization) was used. Morphine was eluted from poppy seeds by acidic water through stationary phase activated aluminum oxide. Poppy seed samples were collected from 13 provinces and 35 different sowing fields of Turkey. The determined morphine contents in poppy seeds were ranged between (9.73 to 37.46) &mu / g/g. Any study was not found in the literatures on determination of total phenolic in poppy seed. In this study, the optimum condition for extraction of polyphenols in poppy seeds was determined and then, total phenolic values were obtained in three different colours seeds by spectrophotometric method. At the end of experiments the total phenolic contents in white, yellow and blue colours poppy seed were found to be 4.44, 3.05 and 3.67 mg/g respectively.

This thesis was aimed to analyze phenol oxidation by the bifunctional catalase/phenol oxidase of the thermophilic fungus Scytalidium thermophilum. Several reactive oxygen species (ROS) are continuously produced in fungi under oxidative stress. Depending on the nature of the ROS species, some are highly toxic and are rapidly detoxified by various cellular enzymatic mechanisms, including the production of catalase. S. thermophilum produces a novel bifunctional catalase-phenol oxidase (CATPO) which is capable of oxidizing phenolics in the absence of hydrogen peroxide. Phenol oxidases convert phenolic compounds to quinones, which are then polymerized mainly by free- radical mediated reactions. In this study, 14 phenolic compounds were selected according to their different chemical structures and functional properties and were analyzed as substrates of CATPO. Among 14 phenolic compounds, only in catechol, chlorogenic acid, catechin and caffeic acid distinct oxidation products were observed by HPLC. The oxidation products of catechol, caffeic acid, chlorogenic acid and catechin were characterized by LC-ESI-MS. Dimer, trimer, tetramer and oligomer formations were detected. While the maximum conversion efficiency, at 1 hour of reaction, was observed with catechin, minimum conversion efficiency was attained by caffeic acid, under the specified conditions. The oxidation products observed after oxidation of catechol, chlorogenic acid, catechin and caffeic acid by CATPO was compared with the same phenolic compounds oxidation products oxidized by laccase and tyrosinase. CATPO was incapable of oxidizing tyrosinase and laccase-specific substrates tyrosine and ABTS respectively. However, the oxidizing spectrum of substrates indicates that the nature of phenol oxidation by CATPO appears to resemble mainly those of laccase.