Clean Label Solutions to Controlling Lipid Oxidation

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1 Clean Label Solutions to Controlling Lipid Oxidation Eric A Decker Department of Food Science University of Massachusetts, Amherst, USA March 27-28, 2018 Itasca, Illinois, USA

2 Why is Oxidation Important? Off-Flavor Formation: Food Waste Loss of Nutrients: Co-Oxidation Fortification with Bioactive Lipids Formation of Toxic Lipid Oxidation Products Acrolein HNE, HHE Oxidized Sterols

3 MECHANISM OF LIPID OXIDATION Initiation Lag Phase Formation of first free radicals HOOC H Hydrogen Abstraction H Isomerization Step

4 Propagation Addition of Oxygen and Transfer of Free Radical HOOC Pentadiene system from another linoleic acid O O oo H O H O Lipid Hydroperoxide

5 β Scission Reactions Breakdown of lipid hydroperoxides to volatile compounds 9-Hydroperoxide Linoleic Acid Metals HOOC O H O Step 1 HOOC Step 2 A A B O B O HOOC H O octanoate and A H 10 HOOC 11 B nonenal and O 9 H 2,4-decadienal oxononanate

6 How to Control Oxidation

7 Impact of Unsaturation on Susceptibility to Lipid Oxidation 18:1 18:2 18:3 20:4 RELATIVE OXIDIZIBILITY :5

8 Newspapers soaked in linseed oil caused fire due to spontaneous combustion (Hampshire Gazette; Northampton, MA)

9 Changing Fatty Acid Composition to Slow Oxidation This was one of the main reasons for hydrogenation Remove 18:3 but formed trans Interesterified oil Can produce solid fat with low total saturates Little know about impact on oxidation High Oleic Oils 18:1 = 10 times more stable than 18:2

10 High Oleic Oils Oil Oleic (%) Polyunsaturated (%) Canola High Oleic Canola 70 3 Safflower High Oleic Safflower Sunflower High Oleic Sunflower 75 10

11 How to Control Oxidation Oxygen Metals Antioxidants Physical Properties Oxidized Fish Oil

12 Propagation HOOC Pentadiene system from another linoleic acid O O oo Diffusion Limited H O H O

13 Oxygen Removal in Low Moisture Food Headspace oxygen removal only takes seconds 65% Oxygen reduction

14 Impact of Oxygen Concentration on Lipid Oxidation Rates in Emulsions Lipid Oxidation TBARS (mmol/kg oil) TBARS oil) Saturated O 2-40% -77% Storage Time (Days) Storage Time (Days) -58% 93% Reduced O 2 98% Reduced O 2

Removing Oxygen by Sparging or Flushing with Oxygen Dissolved Oxygen (C/C 0 ) 1.2 1.0 0.8 0.6 0.4 0.

15 Removing Oxygen by Sparging or Flushing with Oxygen Dissolved Oxygen (C/C 0 ) Min AOX Effect Meaningful AOX Effect Nitrogen Sparge Nitrogen Flush *Not a Sealed System Oxidatively Stable MCT O/W Emulsion Nitrogen Purging Time (min) Time (Minutes) Is oxygen removal a viable antioxidant strategy for emulsions?

16 Oxygen Absorbing Films Alternative Oxygen Mitsubishi Reduction Method OMAC Iron based O 2 scavenging incorporated in the food package protective gas barrier (aluminum ) O 2 Outside Package O 2 O 2 O 2 O/W Emulsion PET Iron-based O 2 scavenger Polyolefins

17 Mitsubishi Oxygen Absorbing Film Uses Ferrous Iron to Absorb Oxygen Oxygen removed quickly by film Oxygen Removal stopped lipid oxidation Limitations: Requires liquid for activation Consequences of anaerobic environment

18 What are the Major Factors Influencing Oxidation Rates Oxygen Metals Antioxidants Physical Properties

19 Iron Decomposition of Lipid Hydroperoxides Fe +2 + LOOH Fe +3 + Off Flavors Electron Source e.g. Ascorbate

20 Impact of Chelators on Propanal Formation in Tween 20 stabilized Algal Oil Emulsions Gold Standard

21 Proteins and Peptides as Antioxidants 18 Peroxides (mm) Control 0.5 mg β-lg/g oil 2.5 mg β-lg/g oil 0.5 mg CTH/g oil 2.5 mg CTH/g oil Proteins Time (day) Peptides

22 Iron Chelating of Proteins and Peptides mg/ml β-lg 1 mg/ml CTH 200 [Fe], μm Treatment Limitations = Bitterness

23 Bitterness Scores of Casein Peptides- Glucose Maillard Products Heating time (h) CP / G 1:0.5 CP / G 1:1 CP/G 1:2 CP ±4.6 a, A 70.7±4.8 a, A 68.8±4.9 a, A 72.4±4.8 a, A ±4.1 a, A 62.5±5.2 b, B 60.3±3.2 b, B 69.8±3.6 a, A ±4.5 b, B 51.7±3.7 c, C 50.8±4.8 c, C 68.0±5.3 a, A ±4.3 c, B 44.0±3.4 d, C 45.8±3.8 d, C 69.8±5.2 a, A ±3.4 c, B 40.1±4.0 d, C 40.0±3.4 e, C 71.0±4.9 a, A Decrease Bitterness without Decreasing Antioxidant Activity Limitation = Chelating Activity Lost at ph < 5.0

24 What are the Major Factors Influencing Oxidation Rates Oxygen Metals Antioxidants Physical Properties

25 Free Radical Scavenging Antioxidants CH 3 Act by lowering the energy of free radicals so they are less effective HO H 3 C O H 3 C O CH 3 ROO ROOH CH 3 O CH 3 CH 3 CH 3 CH 3 O CH 3 CH 3 C 16 H 33 H 3 C O C 16 H 33 CH 3 CH 3 CH 3 CH 3 O O CH 3 CH 3 H 3 C O C 16 H 33 H 3 C O C 16 H 33 CH 3 CH 3

26 Antioxidant Location Location, Location, Location????? Antioxidant paradox was described by Porter (1980) A paradox was suggested because polar antioxidant are most effective in bulk oils while nonpolar antioxidants are best described in oilin-water emulsion

27 Emulsified Oil Nonpolar antioxidant Polar antioxidant

28 CH 3 Nonpolar CH 3 CH 3 CH 3 H 3 C O CH 3 OH CH 3 α-tocopherol CH 3 HO CH 3 O Polar H 3 C O CH 3 Trolox OH

29 Tocopherol = Nonpolar Trolox = Polar Bulk Corn Oil (Huang et al., 1996)

30 Trolox = Polar Tocopherol = Nonpolar Emulsified Corn Oil (Huang et al., 1996)

31 Bulk Oil

32 Antioxidant Activity in Association Colloids Lipid Hydroperoxides (mmol/ Kg oil) Blank (SSO) SSO w/ 1000 um DOPC SSO w/ 1000 um DOPC +10 um Trolox SSO w/ +10 um Trolox SSO w/1000 um DOPC +100 um Trolox SSO w/ +100 mcirom Trolox Storage time (day) A Lipid Hydroperoxides (mmol/ Kg oil) Blank (SSO) SSO w/ 1000 um DOPC SSO w/ 1000 um DOPC +10 um TOC SSO w/ +10 um TOC SSO w/ 1000 um DOPC +50 um TOC SSO w/ +50 um TOC SSO w/ 1000 um DOPC +100 um TOC SSO w/ +100 um TOC Storage time (day) A More Polar Trolox is more effective than Tocopherol

33 Tocopherols Tocopherols are nonpolar antioxidants α-tocopherol is not a very good antioxidant in many foods Mixed tocopherols are a by product of oil refining Contain all tocopherol homologs Tocopherol combinations work better than individual tocopherols

34 Effect of α-tocopherol and Mixed Tocopherol Isomers (500 ppm) on the Oxidative Stability of Whey Protein- Stabilized Algae Oil-in-Water Emulsions at ph 3.0 Too may syllables??

35 Rosemary Antioxidants Extraction technologies minimize flavors Very versatile in many products contain many compounds of varying polarity Combination of compounds increases activity Never approved as an antioxidant

36 Green Tea Water-soluble so good in bulk/frying oils Must be low in chlorophyll to minimize color and stop prooxidant activity in light Lipid soluble derivative are available that may be better in dispersed lipids (e.g. emulsions) Can reduce metals and be a prooxidant in water based foods

37 Iron Decomposition of Lipid Hydroperoxides Fe +2 + LOOH Fe +3 + Off Flavors Electron Source e.g. Catechins

38 Prooxidant and Antioxidant Nature of Green Tea Extract Bulk Oil Oil and Water Emulsion Control

Natural Antioxidants Acerola cherry High in organic acids, phenols and vitamin C Main antioxidant activity is vitamin C Vitamin C is normally a

39 Natural Antioxidants Acerola cherry High in organic acids, phenols and vitamin C Main antioxidant activity is vitamin C Vitamin C is normally a prooxidant in many foods by reducing metals Organic acids could decrease metal interactions with vitamin C switching it from a prooxidant to an antioxidant

Antioxidant Blends Combinations of antioxidants often work better than individual antioxidants Antioxidant regeneration Different physical locations Blends are offered by

40 Antioxidant Blends Combinations of antioxidants often work better than individual antioxidants Antioxidant regeneration Different physical locations Blends are offered by many commercial vendors Often done with expensive antioxidants (aceroloa) to decrease concentrations and control cost Can make for complicated labels with many ingredients

41 What are the Major Factors Influencing Oxidation Rates Oxygen Metals Antioxidants Physical Properties

42 Attack Lipid Fe 2+ ROOH RO Fe 2+ ROOH = Fatty Acid Peroxide RO = Alkoxyl Radical

43 Natural Emulsifiers Quillaja saponin Free Radical Scavenging Properties

44 Oxidation in Nanoemulsions with Different Emulsifiers Quillaja Saponin

45 Free Radical Scavenging Activity of Emulsifiers Surfactant ORAC Tween ± 0.1c SDS 0.5 ± 0.1d Lecithin 5.4 ± 0.2b Q-Naturale 55.6 ± 1.2a Interfacial Antioxidant

46 Water Activity Lipid oxidation is strongly influence by water activity Even small changes in aw could extend shelf-life

47 Sugars as Antioxidant Chemical or Physical (a w ) Activity Control Glucose = Reducing Sugar (1.6%) is more effective

48 Sugar compared to Synthetic Antioxidants Maltose has similar activity with much less sweetness

49 Conclusions Lipid oxidation products are becoming a growing public health concern Fish oil capsules Frying oils Clean label antioxidant strategies could include: Better Control of Oxygen Novel Metal Chelators Naturally Occurring Free Radical Scavengers Manipulation of Physical Properties

How to increase oxidative stability in fats and oils

How to increase oxidative stability in fats and oils 2015. 04. 27. Department of Food Science and Biotechnology, Sungkyunkwan University JaeHwan Lee 1 2 Sungkyunkwan University Founded in 1398 as the highest