The Effect of Plant Based
Extracts in Fat and Oil Systems
William Schroeder, Ph.D.
Kemin Food Technologies
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Agenda
• Antioxidative properties of plant-derived
extracts
• Case Studies
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Impact of Oxidation
• Undesirable chemical change that may impact
flavor, aroma, nutritional quality and even
texture
• Vitamins and other nutrients partially or entirely
destroyed by highly reactive intermediates
• Oxidized fats interact with protein and
carbohydrates
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
What are antioxidants
• Molecules that inhibit the oxidation of fats, oils
and lipid molecules
• Delay oxidation (rancidity) by sacrificing
themselves rather than allowing the oxidation of
the fats
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Oxidation Process
TERMINATION PHASE
(Partly) oxidized
lipids
R-C=C-CH-R’
I
H
Chain Reaction
• Oxidative stress
• Reduction of
nutritional value
OO •
I
R-C=C-CH-R’
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T (°C)
Cu++ Fe++
Light (hn)
INITIATION PHASE
•
R-C=C-CH-R’
O2
PROPAGATION
PHASE
For use in Brazil
Modes of Action
Chelator
Chain breaking
Antioxidants
(radical quenchers)
R-C=C-CH-R’
I
H
Chain Reaction
• Oxidative stress
• Reduction of
nutritional value
T (°C)
Cu++ Fe++
Light (hn)
OO •
I
R-C=C-CH-R’
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
•
R-C=C-CH-R’
O2
Oxygen Scavenger
For use in Brazil
Time-Course curves of antioxidation
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Types of Antioxidants
Origin
Type of
Antioxidant
Natural
Synthetic
Chelator
Citric acid
Phosphoric acid, EDTA
Oxygen
scavenger
Ascorbic acid
Chain breaking
AO
Tocopherols,
Rosemary Extract
Sulphite
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
TBHQ, BHA, BHT
For use in Brazil
PLANT-DERIVED ANTIOXIDANTS
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Tocopherols
Chemical Structures of Natural Tocopherol Homologues
CH3
CH3
O
CH3
 Tocopherol
Mol. Wt. = 430
CH3
(CH2CH2CH2CH)3CH3
HO
CH3
CH3
CH3
O
Increasing
Vitamin E
Activity
 Tocopherol
Mol. Wt. = 416
CH3
(CH2CH2CH2CH)3CH3
HO
CH3
CH3
 Tocopherol
Mol. Wt. = 416
CH3
O
CH3
CH3
(CH2CH2CH2CH)3CH3
HO
CH3
CH3
O
Tocopherol
Mol. Wt. = 402
Increasing
Antioxidant
Activity
CH3
(CH2CH2CH2CH)3CH3
HO
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For use in Brazil
Tea polyphenols
Catechins are one of the active ingredients well known to be present in green tea. They
represent a group of compounds of flavan-3-oils subclass of flavenoids, that donate their
phenolic H to quench free radicals
(-)-epicatechin
(+)-catechin
EGCG
Image source: Frankel, E.N. Lipid Oxidation, p. 156. (1998) Oily Press, Dundee, Scotland
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Phenolic Diterpenes from
Rosemary Extract
O
Carnosic acid
Carnosol
Like other antioxidants, they donate their phenolic H to quench free radicals. The phenolic
diterpenes are detectable in treated foods.
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Controlled Supply Chain is . . .
Consistent Availability
Kemin is one of the most vertically integrated suppliers of
rosemary extract based products in the industry.
Breed
Grow
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Extract
Formulation
For use in Brazil
Kemin’s Rosemary Breeding Process
Search for Genetic
Variation
Key screening criteria
Screen
Breeding
Antioxidant Activity
Biomass
Screen
Winter Hardiness
Optimize Selected
Clonal line(s)
Propagation
Agronomic Scale-up
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For use in Brazil
Application of Rosemary
Extract For Stabilizing
Margarines
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For use in Brazil
Materials and Methods
• Margarine had approximately 45% fat content
• Treatments:
o Untreated
o Tocopherol treatment
o Rosemary extract treatment
• Stored at 10°C for 9 months.
• Measurements
o
Peroxide values
o
p-anisidine
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Data – Peroxide Values (PV)
PV meq O2 / kg sample
50
Negative
Untreatedcontrol
1000
ppm FORTIUM
Tocopherol
TreatmentMTD10
40
1000
ppm FORTIUM
R20
Rosemary
Extract Treatment
30
20
10
0
0
30
60
90
120
150 180 210 240
Time (days of storage)
270
300
330
360
• Increasing trend of peroxides was observed in samples stored at 10 °C.
• Samples treated with Rosemary Extract demonstrated much lower PV throughout the study
(below the cause of concern - 5 meq O2/kg)
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
TL-11-00062
For use in Brazil
Data – p-anisidine Values (AV)
15
Negative
Untreatedcontrol
Tocopherol
TreatmentMTD10
1000
ppm FORTIUM
p-anisidine value
1000
ppm FORTIUM
R20
Rosemary
Extract Treatment
10
5
0
0
30
60
90
120
150
180
210
240
Time (days of storage)
270
300
330
360
• Samples treated with Rosemary Extract showed consistently lower AV throughout
study compared to rest of the treatments and maintained below failure threshold of 10.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
TL-11-00062
For use in Brazil
Key Conclusions
• Chemical analysis over 9 months at 10°C showed the
rosemary extract treatment had superior performance
• Sensory showed the Rosemary Extract treatment
maintained the same sensory characteristics as
positive control (TBHQ)
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
TL-11-00062
For use in Brazil
Application of Rosemary
Extract for the stabilization
Marine Oils
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Materials and Methods
• Treatments (18/12 marine oil):
o Untreated
o Positive control (0.025% dl-alpha-tocopherol + 0.015% TBHQ +
0.01% BHT)
o 0.2% Rosemary extract, ascorbyl palmitate and tocopherols (RAPT)
o 0.5% RAPT
o 0.8% RAPT
• OSI, Alkenal Values and Malonaldehyde Levels tested
• Stored for 8 weeks.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Induction Time of Marine Oil
60.00
Induction time (h)
50.00
40.00
Negative
control
Negative Control
Positive
control (*)
Positive Control
30.00
0.2%
FORTIUM RPT40
0.2% RAPT
0.5%
FORTIUM RPT40
0.5% RAPT
20.00
10.00
0.00
0.8%
FORTIUM RPT40
0.8% RAPT
* Positive control consists of: 0.025% dlalpha-tocopherol + 0.015% TBHQ + 0.01%
BHT.
• Oxidative stability of marine oil was significantly increased by the combo treatment of Rosemary
Extract, Ascorbyl Palmitate and Tocopherols (RAPT) versus the untreated control.
• This blend was able to match the performance of the positive control (tocopherol + synthetics)
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Alkenal Levels of Marine Oil
800
Alkenals (nmol/mL)
700
600
500
Negative control
Control
Negative
Positive control
Control(*)
Positive
400
0.2% FORTIUM
RAPT
0.2%
RPT40
0.5%
RPT40
0.5% FORTIUM
RAPT
0.8%
RPT40
0.8% FORTIUM
RAPT
300
200
100
* Positive control consists of:
0.025% dl-alpha-tocopherol +
0.015% TBHQ + 0.01% BHT.
0
0
5
10 15
20
25
30 35
40
45
50 55
60
65
Time (days)
• The alkenal level of the marine oil stayed well below the 500 nmol/ml off-odor/offflavor threshold 8-week study with treatments of 0.5% and 0.8% RAPT blend
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For use in Brazil
Malonaldehyde Levels of
Marine Oil
12
Malonaldehyde (mg/kg)
10
8
Negative control
Control
Negative
Positivecontrol
Control(*)
Positive
6
0.2%FORTIUM
RAPT
0.2%
RPT40
4
0.5%
RPT40
0.5%FORTIUM
RAPT
0.8% FORTIUM RPT40
0.8% RAPT
2
* Positive control consists of: 0.025% dlalpha-tocopherol + 0.015% TBHQ + 0.01%
BHT.
0
0
5
10
15
20
25
30
35
40
45
50
55
60
65
Time (days)
• The 18/12 marine oil treated with RAPT blend stayed fresh as well as the
synthetic, positive control.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Conclusions
• The Rosemary Extract, Ascorbyl Palmitate and
Tocopherol (RAPT blend) is an effective natural
alternative to stabilize marine oils.
• This unique blend enables food companies to protect
their investment in Omega-3 enriched products.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Increasing The Shelf Life of
a Blend of Palm Fat and
Hydrogenated Rapeseed Oil
at Elevated Storage
Temperature
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For use in Brazil
Overview
• Food processors have shifted away from using
saturated animal fats and toward using unsaturated
vegetable oils due to the increased importance of
health and nutrition to consumers.
• Antioxidant systems are an effective way to increase
shelf life of vegetable oils.
• Global vegetable oil market amounts 2.8 billion USD in
2010, representing 1.6 billion liters 1.
1 Datamonitor, October 20, 2010.
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For use in Brazil
Overview
• Tocopherols and specific antioxidant molecules in
rosemary extract can extend shelf life of oils.
• Vegetable oils contain varying levels of naturally
occurring tocopherols which provide some measure of
oxidative stability.
• Adding higher levels of tocopherols may act as a
pro-oxidant to the oil.
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For use in Brazil
Materials and Methods
• Local vegetable oil manufacturer provided a palm fat and
hydrogenated rapeseed oil blend.
• Treatments:
o Untreated
o Synthetic Treatment
o Tocopherol Treatment
o Rosemary Extract + Tocopherol Treatment
• Fat heated to 50°C, then divided into 60 g portions and dosed
with treatment.
• Treatments divided into 6 x 10g aliquots in sealed 15 ml tubes.
• Stored at 50°C for 7 weeks.
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Study Objective
• Extend shelf life of vegetable oils like a blend of palm
oil and rapeseed oil with the addition of an antioxidant
system.
o
Key Facts • Unsaturated fats more susceptible to oxidation.
• Consumers don’t want their foods to include synthetic
ingredients.
• Manufacturers are seeking natural products to maintain
vegetable oil freshness.
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Peroxide values (PV) of the fat
blend during storage at 50°C.
Untreated
Synthetic Treatment
Tocopherol Treatment
Rosemary Extract +
Tocopherol Treatment
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
TBARS of the vegetable fat
blend during storage at 50°C
Untreated
Synthetic Treatment
Tocopherol Treatment
Rosemary Extract +
Tocopherol Treatment
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For use in Brazil
Key Conclusions
• Rosemary Extract in combination with plant-derived
tocopherols can effectively stabilize oxidative rancidity in
vegetable oils without impacting the flavor profile.
• Tocopherols alone were ineffective in stabilizing the fat
blend, as no significant difference was observed between
the untreated fat blend and the straight treatment
tocopherols.
• If a cost-effective option is preferred, the synthetic
treatment would be acceptable.
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Rosemary & Tocopherol Blend
• Oil-soluble
• Delays oxidation = greater shelf-life
• Natural plant extract and plant-derived ingredient which
allows for a label-friendly ingredient
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For use in Brazil
Rosemary, tocopherol blend demonstrated greater oxidative stability
in Aged Soybean Oil vs. Mixed Tocopherols
Mixed Tocopherol
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
Rosemary +Tocopherol
For use in Brazil
Rosemary, tocopherol blend demonstrated greater oxidative
stability in Fresh Soybean Oil vs. Mixed Tocopherols
Mixed Tocopherol
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
Rosemary +Tocopherol
For use in Brazil
There were no color difference between all treatments
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Sensory Test Results
Study Design
• 2 Independent Test Panels
o
o
Panel 1 compared Mixed
Tocopherol (MT) Treated Oil vs.
Untreated Soybean Oil
Panel 2 compared Rosemary
Extract +Tocopherol (TR) Treated
Oil vs. Untreated Soybean Oil
TR
MT
• Rosemary Extract + Tocopherol at 500 ppm had minimal to no effect on the
soybean oil flavor in comparison to the untreated control treatment.
• Mixed Tocopherol plant derived tocopherols at 500 ppm had a significant impact
on the flavor of the soybean oil in comparison to the untreated control treatment.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Key Conclusion
Rosemary Extract in combination with plant-derived
tocopherols can effectively stabilize oxidative rancidity in
vegetable oils without impacting the flavor profile.
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil
Thank You
will.schroeder@kemin.com
www.kemin.com
© Kemin Industries, Inc. and its group of companies 2013. All rights reserved. ®™ Trademarks of Kemin Industries, Inc., U.S.A.
For use in Brazil