University of Massachusetts Amherst ScholarWorks@UMass Amherst Doctoral Dissertations Dissertations and Theses July 2017 UNDERSTANDING THE IMPACT OF OXYGEN CONCENTRATION AND ACTIVE PACKAGING ON CONTROLLING LIPID OXIDATION IN OIL-IN-WATER EMULSIONS David Johnson University of Massachusetts Amherst Follow this and additional works at: https://scholarworks.umass.edu/dissertations_2 Part of the Food Chemistry Commons Recommended Citation Johnson, David, "UNDERSTANDING THE IMPACT OF OXYGEN CONCENTRATION AND ACTIVE PACKAGING ON CONTROLLING LIPID OXIDATION IN OIL-IN-WATER EMULSIONS" (2017). Doctoral Dissertations. 1019. https://doi.org/10.7275/9969797.0 https://scholarworks.umass.edu/dissertations_2/1019 This Open Access Dissertation is brought to you for free and open access by the Dissertations and Theses at ScholarWorks@UMass Amherst. It has been accepted for inclusion in Doctoral Dissertations by an authorized administrator of ScholarWorks@UMass Amherst. For more information, please contact [email protected]. UNDERSTANDING THE IMPACT OF OXYGEN CONCENTRATION AND ACTIVE PACKAGING ON CONTROLLING LIPID OXIDATION IN OIL- IN-WATER EMULSIONS A Dissertation Presented By DAVID RYAN JOHNSON Submitted to the Graduate School of the University of Massachusetts Amherst in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY May 2017 Food Science © Copyright by David R. Johnson 2017 All Rights Reserved UNDERSTANDING THE IMPACT OF OXYGEN CONCENTRATION AND ACTIVE PACKAGING TO CONTROL LIPID OXIDATION IN OIL-IN- WATER EMULSIONS A Dissertation Presented By DAVID R JOHNSON Approved as to style and content by: __________________________________ Eric Decker, Chair __________________________________ David Julian McClements, Member __________________________________ Wesley Autio, Member __________________________________ Hang Xiao, Member __________________________________ Eric Decker, Department Head Department of Food Science ACKNOWLEDGMENTS First and foremost, I would like to thank the University of Massachusetts for maintaining an atmosphere of growth, opportunity, and collaboration that has shaped me into the individual I am today. It truly is a remarkable place. I first stepped foot on this campus nearly 10 years ago, and since then UMass has provided me with amazing opportunities. Leading me in this way, I have been fortunate enough to have great advisers/mentors that took an active role in my education (especially Dr. Eric Decker, Coach Ken O’Brien, & Dr. Julie Goddard). I cannot forget the support of Dr. McClements, Dr. Xiao, and Dr. Autio who asked me thought provoking questions and gave great advice. A special thanks to Jean, Fran, Debbie, and Stacy who have made my graduate student life at UMass much less complicated. I would also like to thank PepsiCo for their sponsorship and the American Oil Chemists’ Society for their support. As well as, the following companies for providing assistance and materials to support academic research: Ocean Optics Inc., DSM Nutritional Products, and Mitsubishi Gas Chemical. The best part about the UMass Food Science Department is the collaboration and that extends to the student relationships as well. I am forever grateful for the help and friendship of Leann Barden, Bingcan Chen, Dan Vollmer, Raffaella Inchingolo, Sibel, Maxine Roman, Dana Wong, Kyle Landry, Fang Tian, Rika Homma, Jen K., Sam, Julia Gisder, Said Toro Uribe, and all of the lab members that taught me something along the way. A special thank you to my family who has always encouraged and supported me in my pursuit of higher education. Go UMass! iv ABSTRACT UNDERSTANDING THE IMPACT OF OXYGEN CONCENTRATION AND ACTIVE PACKAGING ON CONTROLLING LIPID OXIDATION IN OIL- IN-WATER EMULSIONS MAY 2017 DAVID RYAN JOHNSON, B.S., UNIVERSITY OF MASSACHUSETTS AMHERST M.S. UNIVERSITY OF WISCONSIN – MADISON Ph.D., UNIVERSITY OF MASSACHUSETTS AMHERST Directed by: Professor Eric A. Decker Consumer concern over synthetic food antioxidants have led researchers to seek alternative natural, or ‘clean’ label, solutions to prevent lipid oxidation. Unfortunately, natural antioxidants are often not as effective as their synthetic counterparts. As a result, there remains a need to develop active packaging strategies and maximize current antioxidant strategies in food applications. Active packaging, or packaging that has a function beyond being an inert barrier, is an attractive strategy to limit lipid oxidation in foods. Active packaging performs the work of an antioxidant without appearing on the package label. The work presented here builds upon active packaging development as a means to control prooxidant metals in oil- in-water (O/W) emulsions. A metal-chelating active packaging material was designed and characterized, in which biomimetic poly(hydroxamic acid) (PHA) metal-chelating moieties were grafted from the surface of a common industry used plastic, poly(ethylene terephthalate) or PET. Surface characterization of the plastic film by spectroscopy and scanning electron microscopy (SEM) revealed successful grafting and conversion of the v plastic to contain metal chelating group on the surface. Metal analysis and lipid oxidation studies demonstrated the activity of the PHA grafted PET films to inhibit metal-promoted oxidation in acidified O/W emulsions. Oxygen removal from food packaging is another practical solution to stabilize foods without additives. Indeed, manufacturers have been using this technique for decades, however there is little evidence to how much oxygen needs to be removed to provide meaningful increases in oxidative stability. Results from this research suggest that the oxidative stability of 1% O/W emulsions can be extended by reducing system oxygen by ~58%, but to have a meaningful antioxidant impact greater than ≥93% oxygen removal is required. Further investigation into simulated commercial oxygen removal strategies (e.g., nitrogen displacement of oxygen and ascorbic acid) demonstrated that current industrial strategies are lacking and need to be optimized in order to enhance stability against lipid oxidation. Incorporating both strategies, active packaging and oxygen removal, a commercial oxygen scavenging packaging was tested in its ability to reduce packaged oxygen, inhibit lipid oxidation in O/W emulsions, and stabilize oxygen-sensitive vitamins. Dissolved and headspace oxygen measurements determined the material’s ability to scavenge >95% system oxygen across conditions such as pH, sodium chloride, and fat content. Active oxygen scavenging packaging was able to inhibit lipid oxidation in O/W emulsions as well as preserve Vitamin E and Vitamin C in model solutions. This work demonstrates that active packaging and oxygen reduction are promising strategies that warrant more research in their ability to help achieve ‘clean label’ solutions to prevent lipid oxidation in foods. vi TABLE OF CONTENTS Page ACKNOWLEDGMENTS ................................................................................................. iv ABSTRACT ........................................................................................................................ v LIST OF TABLES ........................................................................................................... xiii LIST OF FIGURES ......................................................................................................... xiv LIST OF SCHEMES...................................................................................................... xviii LIST OF COMMON ABBREVIATIONS ...................................................................... xix CHAPTER 1. INTRODUCTION .......................................................................................................... 1 2. LITERATURE REVIEW: THE ROLE OF OXYGEN IN LIPID OXIDATION REACTIONS ...................................................................................................................... 5 2.1 Abstract ..................................................................................................................... 5 2.2 Introduction ............................................................................................................... 5 2.3 Lipid Oxidation Mechanism ..................................................................................... 7 2.4. Factors that Influence Lipid Oxidation .................................................................... 8 2.4.1 Lipid Compositions ............................................................................................. 8 2.4.2 Minor Components ............................................................................................. 9 2.4.3 Temperature ...................................................................................................... 12 2.5 Oxygen Species ....................................................................................................... 13 2.5.1 Triplet Oxygen ................................................................................................. 13 2.5.2 Reactive Oxygen Species ................................................................................. 15 2.5.3 Singlet Oxygen................................................................................................. 16 2.6 Oxygen in Foods Containing Lipids ....................................................................... 19 vii 2.6.1 Oxygen Location .............................................................................................. 19 2.7. The Effect