Eric A. Decker

Antioxidant Activity of Proteins and Peptides

Proteins can inhibit lipid oxidation by biologically designed mechanisms (e.g. antioxidant enzymes and iron-binding proteins) or by nonspecific mechanisms. Both of these types of antioxidative proteins contribute to the endogenous antioxidant capacity of foods. Proteins also have excellent potential as antioxidant additives in foods because they can inhibit lipid oxidation through multiple pathways including inactivation of reactive oxygen species, scavenging free radicals, chelation of prooxidative transition metals, reduction of hydroperoxides, and alteration of the physical properties of food systems. A proteins overall antioxidant activity can be increased by disruption of its tertiary structure to increase the solvent accessibility of amino acid residues that can scavenge free radicals and chelate prooxidative metals. The production of peptides through hydrolytic reactions seems to be the most promising technique to form proteinaceous antioxidants since peptides have substantially higher antioxidant activity than intact proteins. While proteins and peptides have excellent potential as food antioxidants, issues such as allergenicity and bitter off-flavors as well as their ability to alter food texture and color need to be addressed.

Structural Design Principles for Delivery of Bioactive Components in Nutraceuticals and Functional Foods

There have been major advances in the design and fabrication of structured delivery systems for the encapsulation of nutraceutical and functional food components. A wide variety of delivery systems is now available, each with its own advantages and disadvantages for particular applications. This review begins by discussing some of the major nutraceutical and functional food components that need to be delivered and highlights the main limitations to their current utilization within the food industry. It then discusses the principles underpinning the rational design of structured delivery systems: the structural characteristics of the building blocks; the nature of the forces holding these building blocks together; and, the different ways of assembling these building blocks into structured delivery systems. Finally, we review the major types of structured delivery systems that are currently available to food scientists: lipid-based (simple, multiple, multilayer, and solid lipid particle emulsions); surfactant-based (simple micelles, mixed micelles, vesicles, and microemulsions) and biopolymer-based (soluble complexes, coacervates, hydrogel droplets, and particles). For each type of delivery system we describe its preparation, properties, advantages, and limitations.

Endogenous skeletal muscle antioxidants

Skeletal muscle is susceptible to oxidative deterioration due to a combination of lipid oxidation catalysts and membrane lipid systems that are high in unsaturated fatty acids. To prevent or delay oxidation reactions, several endogenous antioxidant systems are found in muscle tissue. These include alpha-tocopherol, histidine-containing dipeptides, and antioxidant enzymes such as glutathione peroxidase, superoxide dismutase, and catalase. The contribution of alpha-tocopherol to the oxidative stability of skeletal muscle is largely influenced by diet. Dietary supplementation of tocopherol has been shown to increase muscle alpha-tocopherol concentrations and inhibit both lipid oxidation and color deterioration. Dietary selenium supplementation has also been shown to increase the oxidative stability of muscle presumably by increasing the activity of glutathione peroxidase. The oxidative stability of skeletal muscle is also influenced by the histidine-containing dipeptides, carnosine and anserine. Whereas carnosine and anserine are affected by diet less than alpha-tocopherol and glutathione peroxidase, their concentrations vary widely with species and muscle type. In pigs, beef, and turkey muscle, carnosine concentrations are greater than anserine, while the opposite is true in rabbit, salmon, and chicken muscle. Anserine and carnosine are found in greater concentrations in muscle high in white fibers, with chicken white muscle containing over fivefold more anserine and carnosine than red muscle. Anserine and carnosine are thought to inhibit lipid oxidation by a combination of free radical scavenging and metal chelation.

Role of Physical Structures in Bulk Oils on Lipid Oxidation

Lipid oxidation is important to food manufacturers especially when they increase unsaturated lipids in their products to improve nutritional profiles. Unfortunately, the number of antioxidants available to food manufacturers to control oxidative rancidity is limited and the approval of new antioxidants is unlikely due to economic barriers in obtaining government approval for new food additives. Therefore, new antioxidant technologies are needed for food oils. This paper reviews the current knowledge of lipid oxidation in foods with emphasis on how physical properties of food systems impact oxidation chemistry. In particular, the role of association colloids in bulk oils on lipid oxidation chemistry is discussed in an attempt to understand mechanisms of oxidation. Increasing the understanding of how physical properties impact lipid oxidation could lead to the development of novel antioxidant technologies that not only protect the oil against oxidation and increase shelf-life but also allow food manufacturers to include more nutritionally beneficial fatty acids in their products.

Factors Influencing the Chemical Stability of Carotenoids in Foods

In recent years, a number of studies have produced evidence to suggest that consuming carotenoids may provide a variety of health benefits including a reduced incidence of a number of cancers, reduced risk of cardiovascular disease, and improved eye health. Evolving evidence on the health benefits of several carotenoids has sparked interest in incorporating more carotenoids into functional food products. Unfortunately, the same structural attributes of carotenoids that are thought to impart health benefits also make these compounds highly susceptible to oxidation. Given the susceptibility of carotenoids to degradation, particularly once they have been extracted from biological tissues, it is important to understand the major mechanisms of oxidation in order to design delivery systems that protect these compounds when they are used as functional food ingredients. This article reviews current understanding of the oxidation mechanisms by which carotenoids are degraded, including pathways induced by heat, light, oxygen, acid, transition metal, or interactions with radical species. In addition, several carotenoid delivery systems are evaluated for their potential to decrease carotenoid degradation in functional food products.

Controlling lipid bioavailability through physicochemical and structural approaches.

The bioavailability of particular lipids may be either increased or decreased by manipulating the microstructure and/or physiochemical properties of the foods that contain them. This article reviews the current understanding of the molecular, physicochemical, and physiological processes that occur during lipid ingestion, digestion, and absorption, and then discusses some approaches that food scientists may use to control these processes in order to impact the rate or extent of lipid bioavailability. These approaches include controlling the molecular characteristics of the lipid molecules, altering lipid droplet size or interfacial properties, and manipulating food matrix structure and composition. Improved knowledge of the molecular, physicochemical, and physiological processes that occur during lipid ingestion, digestion, and absorption will facilitate the rational design and fabrication of functional foods for improved health and wellness.

Nanoemulsion delivery systems: influence of carrier oil on β-carotene bioaccessibility.

Consumption of carotenoids may reduce the incidences of certain chronic diseases, but their use in foods is currently limited because of their poor water-solubility, low bioavailability and chemical instability. We examined the impact of carrier oil type on the bioaccessibility of β-carotene encapsulated within nanoemulsion-based delivery systems. Oil-in-water nanoemulsions (d<200nm) were formed using a non-ionic surfactant (Tween 20) as emulsifier and long chain triglycerides (LCT), medium chain triglycerides (MCT) or orange oil as carrier oils. The influence of carrier oil type on β-carotene bioaccessibility was established using an in vitro model to simulate the oral, gastric and small intestinal phases of the gastrointestinal tract. The rate and extent of free fatty acid production in the intestine decreased in the order LCT≈MCT≫orange oil; whereas β-carotene bioaccessibility decreased in the order LCT≫MCT>orange oil. The bioaccessibility of β-carotene was negligible (≈0%) in orange oil nanoemulsions because no mixed micelles were formed to solubilise β-carotene, and was relatively low (≈2%) in MCT nanoemulsions because the mixed micelles formed were too small to solubilise β-carotene. In contrast, β-carotene bioaccessibility was relatively high (≈66%) in LCT nanoemulsions. Our results have important implications for the design of effective delivery systems for encapsulation of carotenoids and other lipophilic bioactive components.

Physical and chemical stability of β-carotene-enriched nanoemulsions: Influence of pH, ionic strength, temperature, and emulsifier type

The enrichment of foods and beverages with carotenoids may reduce the incidences of certain chronic diseases. However, the use of carotenoids in foods is currently limited because of their poor water-solubility, high melting point, low bioavailability, and chemical instability. The potential of utilising oil-in-water (O/W) nanoemulsions stabilised by a globular protein (β-lactoglobulin) for encapsulating and protecting β-carotene was examined. The influence of temperature, pH, ionic strength, and emulsifier type on the physical and chemical stability of β-carotene enriched nanoemulsions was investigated. The rate of colour fading due to β-carotene degradation increased with increasing storage temperature (5-55°C), was faster at pH 3 than pH 4-8, and was largely independent of ionic strength (0-500mM of NaCl). β-Lactoglobulin-coated lipid droplets were unstable to aggregation at pH values close to the isoelectric point of the protein (pH 4 and 5), at high ionic strengths (NaCl >200mM, pH 7), and at elevated storage temperatures (55°C). β-Carotene degradation was considerably slower in β-lactoglobulin-stabilised nanoemulsions than in Tween 20-stabilised ones. These results provide useful information for facilitating the design of delivery systems to encapsulate and stabilise β-carotene for application within food, beverage, and pharmaceutical products.

Chain length affects antioxidant properties of chlorogenate esters in emulsion: the cutoff theory behind the polar paradox.

Twenty years ago, Porter et al. (J. Agric. Food Chem. 1989, 37, 615 - 624) put forward the polar paradox stating among others that apolar antioxidants are more active in emulsified media than their polar homologues. However, some recent results showing that not all antioxidants behave in the manner proposed by this hypothesis led us to investigate the relationship between antioxidant property and hydrophobicity. With a complete homologous series of chlorogenic acid esters (methyl, butyl, octyl, dodecyl, hexadecyl, octadecyl, and eicosyl), we observed in emulsified medium that antioxidant capacity increases as the alkyl chain is lengthened, with a threshold for the dodecyl chain, after which further chain extension leads to a drastic decrease in antioxidant capacity. The antioxidant capacity evaluation in emulsion was possible using a newly developed conjugated autoxidizable triene (CAT) assay, which allows the assessment of both hydrophilic and lipophilic antioxidants. The nonlinear behavior was mainly explained in terms of antioxidant location since it was found from partition analysis that the dodecyl ester presented the lowest concentration in the aqueous phase and also that the quantity of emulsifier drastically changes the partition of antioxidant. In addition, this nonlinear influence was connected to the so-called cutoff effect largely observed in studies using cultured cells. Taken together, these different results allow one to make the proposal of a new scenario of the behavior of phenolic compounds in emulsified systems with special emphasis on the micellization process. Finally, in the CAT system, the polar paradox appeared to be the particular case of a far more global nonlinear effect that was observed here.

Relationships between free radical scavenging and antioxidant activity in foods

Numerous attempts have been made to relate the free radical scavenging capacity of compounds to their antioxidant activity in foods even though antioxidant activity is dependent on both physical and chemical properties. The objective of this study was to compare the free radical scavenging activity of various compounds to their ability to inhibit lipid oxidation in foods. The order of free radical scavenging activity of polar compounds was ferulic acid > coumaric acid > propyl gallate > gallic acid > ascorbic acid as determined by a modified oxygen radical absorbance capacity, while the order of nonpolar compounds was rosmarinic acid > butylated hydroxytoluene >or= tert-butylhydroquinone (TBHQ) > alpha-tocopherol as determined by the 2,2-diphenyl-1-picrylhydrazyl assay. Of these compounds, only propyl gallate and TBHQ were found to inhibit lipid oxidation in cooked ground beef as determined by thiobarbituric acid reactive substances, while only propyl gallate, TBHQ, gallic acid, and rosmarinic acid inhibited lipid oxidation in an oil-in-water emulsion as determined by lipid hydroperoxides and headspace hexanal. These data indicate that the free radical scavenging assays tested have limited value in predicting the antioxidant activity in complex foods.