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AN ABSTRACT OF THE DISSERTATION OF Jungmin Lee for the degree of Doctor of Philosophy in Food Science and Technology presented January 13. 2004. Title: The Blueberry: Composition Anthocyanins. And Polyphenolics. Abstract approved: Signature redacted for privacy. .4 Ronald E. Wroistad Frozen blueberries were pilot-plant-processed into juice and concentrate by 2 treatments (heat and SO2), and a control. Qualitative, and quantitative anthocyanin and polyphenolic content were monitored after each processing step. Major losses occurred after the initial processing steps. Juice processing by-product contained a substantial amount of anthocyanins and polyphenolics (>42% and >15%, respectively of the starting material), which indicated they remained a good source for further extraction. Commercial juice processing enzymes (n=9) and other extraction methods were evaluated for extraction of anthocyanins and dietary antioxidants from blueberry skins and wholeberries on a bench-top scale. Blueberries were manually separated into peels, flesh, and seeds. The fractions were evaluated for (qualitative and quantitative) anthocyanin (ACY) and polyphenolic (TP) content, and antioxidant capacity. Blueberry skins had the greatest antioxidant capacity .with the highest ACY and TP content, followed by flesh, and then seeds. The polyphenolic profiles were different in each of the three fractions. High performance liquid chromatography (HPLC), electrospray mass spectrometry (ES-MS), and liquid chromatography mass spectrometry (LC-DAD-MS) were used in identifying the individual anthocyanins. LC-DAD-MS was an invaluable tool in identification of the individual anthocyanins. Four Pacific Northwest native huckleberries (n>38 populations) were collected to compare their ACY and TP content to 'Rubel', which is an important criterion for breeding programs or commercialization. The ACY content of all huckleberry samples analyzed ranged from 101 to 563mg/lOOg (cyanidin3-glucoside equivalents), while the TP varied from 367 to 1286mg/bOg (gallic acid equivalents). The HPLC profile of the individual anthocyanins and phenolics of some of the huckleberries differed in the amounts of delphinidin, cyanidin, and malvidin glycosides. A collaborative study following the guidelines of AOAC International was conducted to validate the pH differential method for determining total monomeric anthocyanin pigment, as an AOAC approved method. Eleven collaborators evaluated seven Youden pairs of test samples. The results (Horrat values1.33) indicated that the method met the objective of determining ACY content of liquid samples, and was recommended to be adopted Official First Action. The Blueberry: Composition, Anthocyanins, And Polyphenolics. by Jungmin Lee A DISSERTATION submitted to Oregon State University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Presented January 13, 2004 Commencenient June 2004 ACKNOWLEDGEMENTS I definitely could not have made it without the support and encouragement surrounding me. I want to express my sincere gratitude to Ron Wrolstad. He has given me unconditional backing through the years I have been in the Food Science department. I could not have made it without him. I would like to thank Bob Durst for his unreserved assistance, encouragement, and friendship. My labmates, and visiting scientists, helped me with their advice, camaraderie, and just making time at work fun: Lucho Rodriguez-Saona, Monica Guisti, Xiaoling Dong, JoLynne Wightman, Matt Glaser, Ling Wen, Kjersti Aaby, Feryal Karadeniz, Florian Stintzing, Angela Stintzing, and Andreas Schieber. I want to thank my conm-ijttee members: Chad Finn, Jim Kennedy, Charles Boyer, and Cliff Pereira. Chad Finn and Jim Kennedy really went out of their way to help me. I would also like to thank the Food Science department faculty, staff, and OSU / USDA friends for their endless help. Special thanks go to Anita Brown, lola Williams, Christina Hull, Linda Dunn, Rosanna Leeson, Jan Carison, Anne Adams, Dan Smith, Brian Yorgey, Boyd Wilcox, Jeff Clawson, James Batdorff, Seojin Chung, Mel Powell, 1mm Tsai, Mona Nataprawira, Rhoda Sithole, Sandra Sandra, Chunran Han, Judy Briggs, Anne Plotto,Panida Pongviratchai, Keith Kiesk, Heesup Kim, Jae Park, Ted Mackey, Kim Hummer, Don Griffin, and Rosie Hopkins I would like to thank the Northwest Center for Small Fruit Research, USDA competitive grant, and the Oregon Blueberry Commission for their support. I want to acknowledge my industry and AOAC collaborators: John Dysart, Ken Stewart, David Kuenzi, Bob Britto, Scott Brix, David Hammond, Sam Grubb, Jonathan Haché, Francois Paquette, Dana Krueger, Alexandra Ryabkova, Steve Kupina, JoLynne Wightman, Grete Skrede, Bent Martinsen, Tom Eisele, Tom Miller, Hans Hofsommer, Susanne Koswig, Uwe Trenn, Susan Martin, Karen Barnes, Annie NG, Joanna Lynch, and many others who have contributed to this work. I would like to thank firms and organizations that supported our research: Kerr Concentrate, Inc., Canandaigua Wine Co., Fall Creek farm and nursery, Inc., Van Cleave Farms, AB enzyme, DSM Food Specialties USA, Inc., Novozymes, Valley Research, Inc., The J. M. Smucker Co, and many others. I especially want to thank Mark Redhead for his love, patience, and encouragement. And finally, I thank all my friends and family: Sherry Clark, Mona Nataprawira, Patrick Cornet, Minami Watanabe, Younhee Kim, Juhee Lee, Mel Powell, The Coopers, Seojin Chung, Scott Redhead, Kjersti Aaby, Joan Redhead, and the ODFW Fish Pathology gang for their support. CONTRIBUTION OF AUTHORS Ronald E. Wroistad has contributed to the experimental design, data analyses, and writing of each chapter. Robert W. Durst was involved in juice and concentrate processing for chapter 3 and helped in data collection and analyses for chapter 7. Chad E. Finn of USDA-ARS (Corvallis, OR) was involved in the experimental design, cultivar selection, data interpretation, and writing of chapters 5 and 6. Cliff Pereira, Kerstine Carter, and Joseph Scherer of the department of Statistics (Oregon State University, Corvallis) were involved in the experimental design of extraction experiments in chapter 4. Donald A. Griffin of the Department of Environmental and Molecular Toxicology (Oregon State University, Corvallis) performed the ES-MS analysis in chapter 3. Deborah Hobbs of the Linus Pauling Institute (Oregon State University, Corvallis) conducted the antioxidant activity measurements for samples in chapters 4 and 6. TABLE OF CONTENTS Page Chapter 1. Introduction . 1 Chapter 2. Literature Review 3 Health benefits of blueberries 3 Blueberry statistics 8 Natural antioxidant extraction of residual berry sources 14 Quantitative analysis of anthocyanins 15 References . 21 Chapter 3. Impact of Juice Processing on Blueberry Anthocyanins and Polyphenolies: Comparison of Two Pretreaments 33 Abstract . 34 Introduction 34 Materials and Methods .. 36 Plant material 36 Reagents and standards 36 Juice processing 36 Pigment extraction 39 Total monomeric anthocyanin and % polymeric color content of samples 39 Anthocyanin and polyphenolic sample preparation 40 Alkaline hydrolysis 40 HPLC separation of anthocyanins and polyphenolics 41 Electrospray mass spectroscopy (ES-MS) of anthocyanins 42 Determination of free sulfur dioxide (SO2) 42 TABLE OF CONTENTS (Continued) Page Color measurements 42 Statistical analysis 43 Results and Discussion . 43 Characterization of bluebeny anthocyanins 43 Changes in anthocyanin composition during juice processing 45 Anthocyanin profile changes from processing 49 Total monomeric anthocyanin, % polymeric color, and color measurements 50 SO2 levels and pH 51 Characterization of blueberry polyphenolics 52 Changes in polyphenolics during juice processing 55 Conclusions 57 Acknowledgements 58 References 58 Chapter 4. Extraction of Anthocyanins and Polyphenolics from Blueberry Processing Waste ..63 Abstract 64 Introduction . 64 Materials and Methods .. 65 Plant material .. 65 Reagents, standards, and enzymes 66 Enzyme evaluation .. 67 Extraction experiments 68 TABLE OF CONTENTS (Continued) Page Sample preparation 69 Determination of total anthocyanins, % polymeric color, and total phenolics 69 Purification of anthocyanins and polyphenolics 70 Determination of antioxidant activity 71 Anthocyanin and polyphenolic analyses by HPLC-DAD 72 Electrospray mass spectroscopy (ES-MS) of anthocyanins 73 LC-DAD-MS of anthocyanins 73 Statistical analyses 74 Results and Discussion 74 Anthocyanins, phenolics, and antioxidant activity of whole berry and their fractions 74 Evaluation of juice processing enzymes 76 Extraction experiments 81 'Rubel' anthocyanin profile 87 Polyphenolics profile 92 Conclusions .. 96 Acknowledgements 96 References 97 Chapter 5. Anthocyanin Pigment and Total Phenolic Content of Three VacciniumSpeciesNativetothePacificNorthwestof North America 102 Abstract .. 103 Introduction 103 TABLE OF CONTENTS (Continued) Page Materials and Methods . 106 Plant material 106 Extraction 107 Determination of total anthocyanins and total phenolics 111 HPLC separation of anthocyanins 111 Statistical analyses 112 Results and Discussion 112 Conclusions ... 120 Acknowledgements 121 References 121 Chapter 6. Comparison of Anthocyanin Pigment and other Phenolic Compounds of Vaccinium membranaceum and V. ovatum Native to the Pacific Northwest of North America 124 Abstract .. 125 Introduction . 125 Materials and Methods .. 127 Plant material 127 Reagents and standards 127 Extraction 128 Berry size, titratable acidity (TA), pH, and °Brix 128
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    Escuela De Posgrado Maestría En Agronegocios

    UNIVERSIDAD NACIONAL AGRARIA LA MOLINA ESCUELA DE POSGRADO MAESTRÍA EN AGRONEGOCIOS “ESTRATEGIAS DE MERCADO PARA FOMENTAR LA EXPORTACIÓN DE ARÁNDANO (Vaccinium spp.) DESDE LIMA A ESTADOS UNIDOS A PARTIR DEL 2017” Presentada por: JULIA ESTHER GAMARRA SOLÓRZANO TESIS PARA OPTAR EL GRADO DE MAGISTER SCIENTIAE EN AGRONEGOCIOS Lima - Perú 2016 UNIVERSIDAD NACIONAL AGRARIA LA MOLINA ESCUELA DE POSGRADO MAESTRÍA EN AGRONEGOCIOS “ESTRATEGIAS DE MERCADO PARA FOMENTAR LA EXPORTACIÓN DE ARÁNDANO (Vaccinium spp.) DESDE LIMA A ESTADOS UNIDOS A PARTIR DEL 2017” TESIS PARA OPTAR EL GRADO DE MAGISTER SCIENTIAE Presentada por: JULIA ESTHER GAMARRA SOLÓRZANO Sustentada y aprobada ante el siguiente jurado: Dr. Pedro Quiroz Quezada Mg.Sc. Luis Espinoza Villanueva PRESIDENTE PATROCINADOR Mto.Prof.CPC. Demetrio Tello Romero Dr. Ampelio Ferrando Perea MIEMBRO MIEMBRO DEDICATORIA La presente tesis la dedico a Dios, por haberme llenado de fuerza y optimismo para cumplir con este objetivo; a mi mamá Julia que ha sido un pilar fundamental en mi formación profesional, por su desprendimiento, sus consejos y por ser un gran ejemplo de perseverancia; a mi esposo Denis por su apoyo incondicional y estar siempre en los momentos difíciles brindándome su amor y su comprensión ; a mi hijo Thiago por su amor y ser el motor de mi vida ; a mi hermana Giuliana por ser siempre mi fortaleza ; a mi primo Tato por haberme siempre orientado a tomar mejores decisiones, a mi Negrita por ser mi segunda madre y motivarme siempre; y a toda mi familia por estar a mi lado en todo momento. Julia. AGRADECIMIENTO A la Universidad Nacional Agraria La Molina, por haberme brindado una formación académica de alto nivel y a los docentes de la Maestría en Agronegocios, por los conocimientos y enseñanzas impartidas durante mi formación post gradual.