Lipid Oxidation in Food and Biological Systems: A Physical Chemistry Perspective

Preface
Acknowledgments
Contents
Part I: Methods to Investigate Lipid Oxidation and Its Inhibition
	Lipid Oxidation in Food Emulsions: Analytical Challenges and Recent Developments
		1 Introduction
		2 Lipid Extraction and Sample Preparation
			2.1 Common Lipid Extraction Methods
			2.2 Limitations of Current Lipid Extraction Methods
			2.3 Considerations Regarding Lipid Extraction from Emulsions
		3 Unravelling Lipid Oxidation Pathways by Magnetic Resonance Spectroscopy
			3.1 Early Assessment of Lipid Oxidation Using ESR Spectroscopy
			3.2 Mechanistic Insight on Lipid Oxidation Using NMR Spectroscopy
		4 Contribution of Minor Lipid Species by Liquid Chromatography Mass Spectrometry
			4.1 Non-volatile Oxidation Products in Oil-in-Water Emulsions
			4.2 Study of Minor Lipid Species: Missing Gap and Perspectives
		5 Assessment of Volatile Lipid Oxidation Products by Headspace Gas Chromatography
			5.1 Profiling of Volatile Organic Compounds to Assess Lipid-Derived off-Odors
			5.2 Analytical Challenges for the Absolute Quantification of VOCs
		6 Probing Lipid Oxidation by Multi-Scale Imaging Techniques (from nm to μm)
			6.1 Electron Microscopy (EM) Studies
				6.1.1 Dry and Cryo-TEM
				6.1.2 Dry and Cryo-SEM
			6.2 Fluorescence Microscopy Studies
				6.2.1 Assessment of Microstructural Impact of Oxidation Using Fluorophores
				6.2.2 Localization of Lipid Oxidation Events
			6.3 Overview of Food Microscopy Methods
		7 Conclusion
		References
	Determining Antioxidant Distributions in Intact Emulsions by Kinetic Methods: Application of Pseudophase Models
		1 Introduction
		2 Computational and Experimental Methods to Determine Partition Constants
		3 Why Are Partition Constants of Antioxidants in Emulsions Valuable? An Example, a Brief Kinetic Analysis of Lipid Oxidation a...
			3.1 Experimental Methods for Determining Partition Constants in Binary Oil-Water and Emulsified Systems
		4 Chemical Kinetic Method: A Unique Physical-Organic Approach for Determining Antioxidant Distributions and Interfacial Molari...
			4.1 Main Assumptions of the Pseudophase Model as Applied to Reactions in Emulsions (Dar et al. 2017; Bravo-Díaz et al. 2015; R...
			4.2 Relevant Equations Derived for the Application of the Pseudophase Model
			4.3 Determining kobs Values in Opaque Emulsions: Monitoring the Reaction Between 16-ArN2+ and AO by Employing Electrochemical ...
			4.4 Determining Antioxidant Partition Constants in Intact Emulsions
		5 Conclusions and Future Perspectives
		References
	Fluorescent Probes for Monitoring Oxidation of Lipids and Assessment of Antioxidant Activity
		1 Introduction
		2 Reactive Intermediates of Peroxidation
		3 Fluorescent Probes for Monitoring Peroxidation
			3.1 Luminescence and Fluorescence
			3.2 Fluorophore Properties
			3.3 Fluorescent Probes: Development, Classification, Mechanisms
			3.4 Conclusions
		References
	Lipid Oxidation in Meat Systems: Updated Means of Detection and Innovative Antioxidant Strategies
		1 Introduction
		2 Lipid Oxidation in Meat Products: Innovative Means of Analysis
			2.1 Assessment of Primary Oxidation Products
			2.2 Assessment of Secondary Oxidation Products
				2.2.1 Malonaldehyde
				2.2.2 Lipid-Derived Volatiles
			2.3 Advanced Methodologies for Lipid Oxidation Assessment: Non-destructive Methods
		3 Lipid Oxidation in Meat Products: Innovative Antioxidant Solutions
			3.1 Ante-Mortem Antioxidant Solutions
			3.2 Post-Mortem Antioxidant Solutions
		4 Future Perspectives
		References
Part II: Lipid Oxidation and Inhibition in Different Systems
	The Underrecognized Role of the Hydroperoxyl (HOO) Radical in Chain Propagation of Lipids and its Implication in Antioxidant A...
		1 Introduction
		2 The HOO Radical
			2.1 Biochemical Role
			2.2 Physico-Chemical Characteristics of HOO
			2.3 Formation of HOO
			2.4 Kinetics of Intra-1,4-HAT
		3 Antioxidant Effects in LOO/HOO Mediated Chain Propagation of Lipids
		4 Synergy of HOO with Antioxidants
			4.1 Synergy of HOO with Phenols and Aromatic Amines
			4.2 Synergy of HOO with Nitroxides and Quinones
		5 Methods to Detect HOO Formation
		6 Conclusions
		References
	Location, Orientation and Buoyance Effects of Radical Probes as Studied by EPR
		1 Introduction
			1.1 Location and Orientation of Probes and Antioxidants in Heterogeneous Systems
			1.2 Cut-off Effects and Probe Orientation
			1.3 A Methodology Based on EPR Spectroscopy to Evaluate the Partitioning of Nitroxide Probes in Micelles
		2 Cut-off Patterns and the Location of Probe/Antioxidant in Heterogeneous Media
		3 Amphiphobic Structure and the Diving-Swan Analogy
		4 Summary and Perspectives
		References
	Lipid Antioxidants: More than Just Lipid Radical Quenchers
		1 Introduction
		2 Prevention of Initiation
			2.1 Metal Complexation and Cycling
			2.2 Singlet Oxygen Quenching
		3 Effects on Propagation
			3.1 Inhibition by Radical Scavenging
				3.1.1 Reactions of Phenol Forms of Antioxidants
				3.1.2 Reactions of Quinone Forms of Antioxidants
			3.2 Shifts in Propagation Pathways
				3.2.1 Modification of Primary Lipid Oxidation Products
					Phenol Reactions that Increase LOOH
					Phenol Reactions that Decrease LOOH
		4 Alteration of Products
			4.1 Formation of Adducts with Lipid Carbonyls
		5 Phenol Effects on System Oxidation Beyond Lipids
			5.1 Phenol Associations with Proteins via Noncovalent Interactions
			5.2 Quinone Covalent Reactions with Proteins
			5.3 Chemical Reactions Not Involving Binding
		6 Summary: What Does This All Mean?
		References
	Effect of Lipophilic and Hydrophilic Thiols on the Lipid Oxidation
		1 Introduction
		2 Glutathione in Lipid Oxidation
		3 Conclusions and Perspective
		References
	Control of Lipid Oxidation in Oil-in Water Emulsions: Effects of Antioxidant Partitioning and Surfactant Concentration
		1 Introduction
		2 Effects of Hydrophobicity on Antioxidant Efficiencies: Phenomenological Observations
			2.1 Determining the Distribution of AOs in Intact Emulsions
		3 Control of Lipid Oxidation with Antioxidants
			3.1 Effects of the Hydrophobicity of the Antioxidant and Emulsifier Concentration on the Distribution of Antioxidants
			3.2 Effects of the Surfactant Concentration
			3.3 Relationships Between the Antioxidant Efficiency and Interfacial Concentrations
		4 Conclusions
		References
	Effects of Emulsion Droplet Size on the Distribution and Efficiency of Antioxidants
		1 Lipid-Based Emulsions
		2 Physical Stability of Emulsions
			2.1 Thermodynamics and Kinetics
			2.2 Physical Destabilization Mechanisms
		3 Oxidative Stability of Emulsions: Lipid Oxidation
			3.1 Brief Description of the Mechanism of Lipid Oxidation and Inhibition by Antioxidants
			3.2 Effects of Droplet Sizes on the Oxidative Stability of Emulsions
		4 Effects of Droplet Size on the Partitioning of Antioxidants in Emulsions
		5 Relationships Between the Antioxidant Efficiencies and the Interfacial Concentrations of AOs in Emulsions and Nanoemulsions
		6 Conclusions and Perspectives
		References
	Nanoemulsions as Encapsulation System to Prevent Lipid Oxidation
		1 Introduction
		2 Nanoemulsions
			2.1 Nanoemulsion Preparation
			2.2 Nanoemulsion Composition
				2.2.1 Emulsifiers
				2.2.2 Lipid Phase
				2.2.3 Aqueous Phase
		3 Nanoemulsions to Prevent Lipid Oxidation
			3.1 Engineering of the Oil-Water Interface
				3.1.1 Interfacial Thickness
				3.1.2 Interfacial Charge
				3.1.3 Emulsifier Location
			3.2 Addition of Antioxidants
		4 Conclusions
		References
	The Effects of Association Colloids on Lipid Autoxidation in Bulk Oils
		1 Introduction
			1.1 Minor Components of Vegetable Oils
		2 Amphiphilic Properties of Minor Oil Components
		3 Formation of Association Colloids in Bulk Oils
		4 Interactions of Antioxidants with Association Colloids
		5 The Effects of Association Colloids on Lipid Autoxidation in Bulk Oils
		6 The Role of Water in the Formation of Association Colloids and its Effects on Lipid Autoxidation in Bulk Oil
		7 Methods Used in Association Colloids Studies
		8 Conclusions
		References
	Antioxidant Activity of Edible Isothiocyanates
		1 From Mustard Oils to Isothiocyanates
		2 Sources of Natural Isothiocyanates
		3 Bioactivity
			3.1 Prooxidant Action
		4 Direct Reactions of Isothiocyanate (N=C=S) Moiety with Radicals
		5 Reactions of ITCs and GSLs with ROS
			5.1 Reaction with Peroxides
			5.2 Reactions of ITCs with Artificial Model Radicals
			5.3 Reactions with Other Radicals
			5.4 Activity at Elevated Temperatures
		6 Conclusions
		References
	Photosensitized Lipid Oxidation: Mechanisms and Consequences to Health Sciences
		1 Introduction
			1.1 Singlet Oxygen as an Initiator
			1.2 Photosensitizer Excited States as Initiators
			1.3 Determinants of Photooxidation Mechanisms and Their Outcomes
		2 Photooxidation Affects the Structure and Properties of Membranes
		3 The Effect of Light-Induced Oxidation on Skin Lipids
		4 Photosensitized Lipid Oxidation in Photodynamic Therapy
		5 Conclusions
		References
Part III: Health, Biological and Nutritional Effects
	Antioxidants in Dentistry: Oxidative Stress and Periodontal Diseases
		1 Introduction
			1.1 Periodontal Diseases
			1.2 Oxidative Stress
			1.3 Reactive Oxygen Species (ROS)
			1.4 Sources of ROS in the Oral Cavity
			1.5 Molecular Targets of ROS: Typical Lifetimes
		2 Mechanisms of Development and Control of Periodontitis
			2.1 Clinical Implications for ROS Involvement in Periodontal Diseases
			2.2 Pathogenesis of Periodontitis: Biomarkers of Oxidative Stress
			2.3 Antioxidants in the Oral Cavity: Antioxidant Treatment of Periodontal Diseases
			2.4 Effects of Diet on Periodontal Diseases and Oxidative Stress
			2.5 Role of Nutrition in Periodontal Health: An Update
		3 Conclusions and Future Perspectives
		References
	Phytosterols as Functional Compounds and Their Oxidized Derivatives
		1 Introduction
		2 Phytosterols in Food Products
		3 Biological Properties of Phytosterols
			3.1 Cholesterol-Lowering Properties of Phytosterols
			3.2 Neuroprotective Properties of Phytosterols
			3.3 Anticancer and Anti-inflammatory Properties of Phytosterols
			3.4 Mechanisms of Phytosterols Absorption
		4 Oxidation of Plant Sterols
			4.1 Autoxidation
			4.2 Photooxidation
		5 Phytosterol Oxidation Products in Foods
		6 Biological Properties of Oxyphytosterols
		7 Other Products Formed During the Oxidation of Phytosterols
			7.1 Volatile Derivatives
			7.2 Dimers, Trimers, Oligomers
		8 Conclusions
		References
	Amino Acids, Amino Acid Derivatives and Peptides as Antioxidants
		1 Introduction
		2 Antioxidant Amino Acids
			2.1 Phenolic Amino Acids
				2.1.1 L-Tyrosine and Its Derivatives
				2.1.2 Hydroxyphenylglycines
			2.2 Other Natural Amino Acids with Antioxidant Properties
			2.3 α,β-Dehydroamino Acids
		3 Amino Acids Coupled with Phenols
		4 Antioxidant Peptides
		5 Antioxidants Targeting the Mitochondria
			5.1 Non-peptidic Mitochondrial Antioxidants
			5.2 Cell Penetrating Peptides
			5.3 Mitochondrial Penetrating Peptides
			5.4 Antioxidant Mitochondrial Penetrating Peptides
		References
	Plant Phenolics as Dietary Antioxidants: Insights on Their Biosynthesis, Sources, Health-Promoting Effects, Sustainable Produc...
		1 Phenolic Compounds in Plant Systems
		2 Plant Phenolic Compounds: Biosynthesis, Dietary Sources, and Health-Promoting Effects
			2.1 Phenolic Acids
			2.2 Lignans
			2.3 Coumarins
			2.4 Stilbenes
			2.5 Flavonoids
				2.5.1 Chalcones
				2.5.2 Flavones
				2.5.3 Flavanones
				2.5.4 Isoflavonoids
				2.5.5 Flavonols
				2.5.6 Flavanols
				2.5.7 Anthocyanins
		3 Plant Phenolics: Production, Extraction, and Lipid Oxidation Prevention
			3.1 Biotechnological Production of PCs
			3.2 Sustainable Extraction of PCs
			3.3 PCs as Preservative Antioxidants in Oil-in-Water Emulsions
		4 Concluding Remarks
		References
	Olive Oil Phenolic Compounds as Antioxidants in Functional Foods: Description, Sources and Stability
		1 Introduction
		2 Olive Phenols
			2.1 Olive Oil Polar Phenols
			2.2 Tocopherols
			2.3 Sources of Olive Polyphenols
			2.4 Stability of Olive Oil Phenolic Compounds under Storage Conditions
		3 The Oxidative Stability of Olive Oil
			3.1 Contribution of Olive Oil Phenolic Compounds to the Oxidative Stability of Bulk Olive Oil
			3.2 Contribution of Olive Oil Phenolic Compounds to the Oxidative Stability of Olive Oil in Multiphase Systems
		4 Application of Olive Phenolic Compounds as Antioxidants in Foods
			4.1 Vegetable Oils
			4.2 Meat Products
			4.3 Dairy Products
			4.4 Bakery Products
		5 Conclusions
		References
	Nutritional and Preservative Properties of Polyphenol-Rich Olive Oil: Effect on Seafood Processing and Storage
		1 Quality Changes of Fish During Processing
		2 Polyphenol-Rich Olive Oil: Nutritional Aspects Related to Human Health
			2.1 Health Effects of the Unsaponifiable Fraction of the Olive Oils
			2.2 Health Effects of the Saponifiable Fraction of the Olive Oils
		3 Polyphenol-Rich Olive Oil: Modifications During Processing and Preservative Behaviour
			3.1 Modifications During Frying
			3.2 Modifications During Other Processing and Model Systems
		4 Preserving Effect of Polyphenol-Rich Olive Oil During Fish Processing and Storage
			4.1 Preserving Effect During Fish Frying
			4.2 Preserving Effect During Fish Canning
		5 Final Remarks and Future Trends
		References