the science of antioxidant selection - saafost · food technologies • delivers innovative,...

© Kemin Industries, Inc. and its group of companies 2015 All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.

The science of

antioxidant selectionDr. Stefaan Van Dyck

Food Technologies EMEA


Topics

• The oxidation process at molecular level

• Measuring shelf life in food matrices

• Prevention of oxidation - selection of the antioxidants.

• Natural plant materials as a sustainable alternative for

synthetic solutions.


History of Kemin

• Founded in 1961 by RW & Mary Nelson

o Independently owned by Nelson family

• 1,800+ employees worldwide

• Business operations in over 90 countries

o Manufacturing facilities located in 8 countries

• Over $600M annual revenue

• Over 200 patents


The oxidation process at

a molecular level


• Why are there 2 types of oxygen and why

do they behave so different?

2S+1 = 2 (0.5+ 0.5) +1 = 3 Triplet oxygen

Triplet and singlet oxygen


Light (hn)

2S+1 = 2 (0) +1 = 1 Singlet oxygen

• Why are there 2 types of oxygen and why

do they behave so different?



3O2

1O2

Shutterstock Images

T°

Insight in the oxidation process


3O2

1O2

Electron spin

Energy level

Nature

Reacts with

Rate C18:1 oxidation

22.4 kcal/mole

electron rich

non-radicals

3 x 104

0 kcal/mole

diradical

radicals

1

http://genchem.chem.wisc.edu/

Dia

ma

gn

etic



RR'H H

RR'

-H

3O2

910

11

1213

9- and 13-hydroperoxide

3O2

R'1O2

910

11

1213

R'

O O

R

H

R

H

9-, 10-, 12- and

13-hydroperoxide

1O2

Reaction of oxygen with lipids


2h in light

0,0

5,0

10,0

15,0

20,0

25,0

30,0

35,0

40,0

2,4-Heptadienal Butenal 2-Heptenal

Oxidation product

AU

C (

Me

ga

un

its

)

Control + S* + S* + BHA + S* + Vit E + S* + b-Caroteneb

3O21O2

3O21O2

3O21O2

• 1O2 quencher has no impact on typical 3O2 degradation products

like hexanal

Effect of antioxidants on 1O2-degradation products


Measuring shelf life in

foods


R-C=C-CH-R’

T (°C)

Cu ++ Fe ++

Light (hn)

IOO

R-C=C-CH-R’•

IH

•

R-C=C-CH-R’

O2Further reaction forming:

Aldehydes and acids (tertiary

reaction products)

Measured with OSI or Rancimat

Oxygen bomb

Peroxide value

AOMTBA, Anisidine-value,

SPME-GC/MS

Polar fraction with SEC or NIR

Overview -starting from the

oxidation cycle

ESR


HighHours80-100OSIAccelerated

MediumWeeks30-50Sensorial,

chemicalStandard

LowMonths25-30Sensorial,

chemical

Shelf life

Stress factorTesting timeTemp. (°C)AnalysisMethod

HighHours80-100OSIAccelerated

MediumWeeks30-50Sensorial,

chemicalStandard

LowMonths25-30Sensorial,

chemical

Shelf life

Stress factorTesting timeTemp. (°C)AnalysisMethod

Oxidation studies


Traditional methods

• Peroxide value

• TBA value / p-Anisidine value

• Polar lipid fraction

• GC-MS headspace of volatiles

Accelerated methods

• AOM (Active oxygen method)

• OSI (Oxidative Stability Index)/Rancimat

• Oxygen bomb

Analysis of lipids


Reference Information

Accelerated Oxidation

• Oxidative Stability Index (OSI) - (AOCS Official Method Cd 12b-92)

• The oil stability index (OSI) method measures the formation of volatile organic acids by monitoring the change

in electrical conductivity when the effluent from oxidizing oils is passed through water

• The oxidation process is accelerated by exposing oil samples to elevated temperatures in the presence of air

or oxygen

• The OSI method differs from ambient storage conditions by using a flow of air and high temperatures to

accelerate oxidation

• Used for antioxidant screening

Conditions

• Substrate: 50% High Oleic Sunflower oil with 50% canola oil

• 3 gram oil sample

• Temperature: 110°C

• Air flow: 10 Liter/ hour


Accelerated Oxidation

Antioxidants tested in 50% high oleic sunflower oil (HSFO) + 50% Canola oil:

• TBHQ dry (Tertiary butyl hydroquinone)

• FORTIUM® GRC30 liquid: gallic acid, rosemary extract and citric acid


Impact of formulation


Polar antioxidants should be used to stabilize apolar lipids !

Polar antioxidants partition at the surface

Drawback : how to introduce polar AO in lipids?

Formulations:

The polar paradox


Oxidation at the interphase

Fe2+

Fe3+

Metal reducing

agent

LOOH

LO

Inactivated by aquaous

phase antioxidant

Inactivated by surface

active antioxidant

Inactivated by lipid

phase antioxidant

React with other lipid

Biopolymer

interfase

Oil Water


The antioxidant toolbox

Green Tea BHA TBHQ BHT

Propyl Gallate

Rosemary

Spearmint Tocopherols

Acerola Citric Acid

Free Radical Scavengers Oxygen Reducer Chelator

http://en.wikipedia.org/wiki/File:2,6-bis(1,1-dimethylethyl)-4-methylphenol.svg

http://en.wikipedia.org/wiki/File:2,6-bis(1,1-dimethylethyl)-4-methylphenol.svg

http://en.wikipedia.org/wiki/File:Propyl_gallate.svg

http://en.wikipedia.org/wiki/File:Propyl_gallate.svg

http://upload.wikimedia.org/wikipedia/commons/3/3a/Rosmarinic_acid.png

http://upload.wikimedia.org/wikipedia/commons/3/3a/Rosmarinic_acid.png

//upload.wikimedia.org/wikipedia/commons/e/e7/L-Ascorbic_acid.svg

//upload.wikimedia.org/wikipedia/commons/e/e7/L-Ascorbic_acid.svg

//upload.wikimedia.org/wikipedia/commons/c/c5/Zitronens%C3%A4ure_-_Citric_acid.svg

//upload.wikimedia.org/wikipedia/commons/c/c5/Zitronens%C3%A4ure_-_Citric_acid.svg


Which extract to choose?

Shutterstock Images


(Anti)oxidation in practice


Food Technologies

• Delivers innovative, market-driven technologies that target the food

industry’s toughest challenges.

Antioxidants…to extend shelf life

Plant-derived

Antioxidants

Plant

ExtractsSynthetic

Food Safety…to control microbial growth

Synthetic Natural


LOW FAT (65%) MAYONNAISE

Conclusion:

The shelf life of mayonnaise could be increased by changing the packaging but NaturFORT™15 L was still required to

reach the desired shelf life

Reference: Kemin Internal Document 14-00002


Shelf-life Extension of Frying Oils

and the Effect on the Fried Product

• Matrix:

o Sunflower oil (SFO)

o High oleic sunflower oil (HOSFO)

o Palm olein (PO)

• Treatment:

o Tocopherols (FORTIUM®TG20)

o Rosemary extract (FORTIUM® RG20)

• Finished product: tortilla crisps

• Accelerated storage, peroxide values

Reference: Kemin Internal Study INF-2011-00007


Effect on the Fried Product

0

10

20

30

40

50

60

70

80

90

100

0 10 20 30 40 50 60

PV

(m

eq/k

g f

at)

Time (days) at 40°C

HO-SFO control

HO-SFO + 0.15% RG20

Palm olein control

Palm olein + 0.15% RG20

SFO control

SFO + 0.15% RG20

Reference: Kemin Internal Study INF-2011-00007


Dairy

Whole fat milk

Shutterstock Image


Whole fat milk

Reference: Kemin Internal Study 15-00045 Development of Ingredients For Delaying Milk Fat Oxidation

0

1

2

3

4

5

6

7

FORTRA 101Dry 25 ppm

FORTRA 101Dry 60ppm

FORTRA 101Dry 120ppm

BHA 1 BHA 2

Me

q / k

g F

at

Figure 1. PV in whole fat milk

Day1 Day4 Day7

“BHA 1” is 200 ppm BHA based on dry weight (the upper legal limit in the European Union)

and “BHA 2” is 200 ppm BHA based on fat weight (the upper legal limit in the United States).


The challenge of

consistency and safety

of plant extracts


Propagation

Agronomic Scale-up

Search for Genetic

Variation

Breeding

Optimize Selected

Clonal line(s)

Screen

Screen

Functionality

Biomass

Key screening criteria

Plant Breeding Program

Reference: Kemin Internal Pictures


Innovation

Microwave drying – patent pending

• Microwave drying

o 4 chambers per line

o Reduces water from 80% to <15%

o Protects flavour and rosmarinic acid

Reference: Kemin Internal Pictures


Plant science & sustainability

• ‘Sustainably Grown’ is one of the most stringent certification

standards, supporting long-term sustainable agricultural

production

• Kemin is the first and one of the only to acquire third-party

‘Sustainably Grown’ certification for rosemary and spearmint

References: Kemin Internal Pictures

SCS global services


THANK YOU FOR

YOUR ATTENTION

Stefaan Van Dyck

[email protected]

www.linkedin.com/in/stevady

Tel: 011 7047261 (JHB)

Tel: 021 9139818 (CPT)

[email protected]

www.Danlink.com

http://www.linkedin.com/in/stevady

mailto:[email protected]

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