Transcript Antioxydants subjects

EUROTIOX
Eurotiox ® , the most cost-effective antioxidant
AUTOXIDATION
•SERIES OF DESTRUCTIVE CHEMICAL
PROCESSES
•OCCURS IN ORGANIC MATERIALS
•CHANGES THE CHEMICAL NATURE OF
AFFECTED MOLECULES
•INCREASINGLY FAST
•ROOM TEMPERATURE REACTION
•CAUSES RANCIDITY IN FATS, OILS
BIOTIN
Eurotiox ® , the most cost-effective antioxidant
Oxidation influenced by:
Moisture:
free water in raw material and feed
Catalysts:
Light:
Temperature:
Contact with air:
Enzymes:
Time:
metals promoting free radical formation,
promotes oxidation
increase oxidation also during cooling
improves peroxide formation
lipase, lipoxygenase
storage time, production
Eurotiox ® , the most cost-effective antioxidant
Aldehydes from Fat Autoxidation
Carbonyls
2-Decenal
2-Undecenal
2-Nonenal
2-Octenal
Hexanal
2-Heptenal
Heptenal
Nonanal
Octanal
2-4=Decadienal
4 cis-Heptenal
4-trans-Heptenal
4 trans, 6-trans Nonadienal
2 trans, 6-cis Nonaienal
Frankel, 1984
Flavours Threshold (ppm)
5.5
4.2
0.1
1.0
0.15
0.63
0.042
0.32
0.068
0.28
0.001
0.32
0.001
0.002
Eurotiox ® , the most cost-effective antioxidant
THE INFLUENCE OF OXIDISED FAT ON
THE MICRO-FLORA IN BROILERS
(11 DAYS)
10
8
6
Fat
Fat + AO
Oxidised Fat
Oxidised Fat + AO
4
2
0
Facult.
Anaerobes
E.coli
Lactobacilli
Eurotiox ® , the most cost-effective antioxidant
TOXIC METABOLITES OF FAT
OXIDATION
Shorten small intestine villi
length
FROM: Poul. Sci. Abstracts (1994) Vol. 73, Suppl. 1, pg 47.
Reduce nutrient adsorption
Eurotiox ® , the most cost-effective antioxidant
Autoxidation and Animal production






Reduced Egg production in laying hens (72%)
(Voreck & Kirehgessner, 1981)
Autoxidation products are cancernogenic
(Morita et al., 1983)
Even low increase in Peroxide Value (>7 meq/kg) has a significant
effect on Feed Conversion Ratio (Cabel et al., 1988)
Rancid Feed has an impact on the gastro-intestinal Structure, Cell
proliferation and intestinal Microflora (Shermer et al., 1995)
Oxidised vegetable oil in Broiler feed reduces growth rate (5%)
(Engberg et al 1996)
Rancid fish oil induced anaemia in Mink, reduced iron absorption
(Borsting et al., 1994)
Eurotiox ® , the most cost-effective antioxidant
Effect of peroxides on broiler
performances (49 days)
University of Arkansas
2,3
2,2
2,1
2
1,9
1,8
1,7
1,6
1,5
FCR
a
Body weight (kg)
ab
+ 4.78 %
c
b
- 6.29 %
0
2
4
Feed Peroxide value (meq/kg feed)
7
Cabel, M. C., P. W. Waldroup, W. D. SHermer and D. F. Calabotta (1989), Poultry Science 67: 1725-1730
Eurotiox ® , the most cost-effective antioxidant
Effect of raw material quality on broiler
performances (56 days)
INTA (Argentina)
Body weight (kg)
2,9
2,7
2,5
a
FCR
a
a
a
a
- 10.69 %
2,3
b
2,1
1,9
a
+ 6.43 %
b
1,7
1,5
2
30
68
120
Meat meal Peroxide value (meq/kg) used in broiler feed
Schang et al. - 1987
Eurotiox ® , the most cost-effective antioxidant
The three stages of OXIDATION
1) Initiation phase
RH -----> R° + H°
Fat molecule
Free radical
2) Propagation phase
R°
+ O2 ----> ROO°
ROO°
+ RH
---->
ROOH
(peroxide)
+
R°
3) Termination phase
ROO° + ROO° ---> stable end products
(aldehydes, ketones, short chain fatty
acids)
Eurotiox ® , the most cost-effective antioxidant
Oxidation Process involving
Oxygen & lipids
temp.
Catalysts
Light
Air
Time
Lipids
FREE
RADICALS
PEROXIDES
+
Damage critical
nutrients
FREE
RADICALS
Oxygen
forms
Aldehydes
Ketons
PEROXIDES
• Reaction with cell membranes
• Toxic for animals
• Destruction of fat soluble vitamins
• Reduction of performances
• Rancidity
• Reduction of feed intake
• En-products absorbed in the body
• Start of in vivo oxidation
Eurotiox ® , the most cost-effective antioxidant
The three stages of OXIDATION
Peroxides value
(meq)
Peroxides, radicals
water
Induction
Oxidation
Polimers, oxidised
fat, acids, aldehides
ketones
Termination period
Eurotiox ® , the most cost-effective antioxidant
Different antioxidants
Free radical scavengers:
Ethoxyquin, BHA, BHT, Propyl Gallate
Chelators:
Citric acid, phosphoric acid
Eurotiox ® , the most cost-effective antioxidant
Differences between antioxidants
Ethoxyquin:
very stable, only feed grade, raw materials
Gallates:
very stable, regenerates ethoxyquin or BHA activity
BHA:
heat stable, mainly food and petfood
BHT:
heat stability problem, repartition problem,
readily broken down in premixes
Eurotiox ® , the most cost-effective antioxidant
Triple Mode of Action
EUROTIOX
1.Citric acid forms reversible bonds with metal pro-oxidants
in the premix and feed to inhibit them from initiating
oxidation
2. Ethoxyquin blocks oxidation by donating hydrogen ions
to free and peroxy radicals formed during the onset
and propagation stages
3. Propyl gallate restores and potentiates ethoxyquin activity
up to 3 times by donating hydrogen ions from its 3 active
sites to oxidised (spent) ethoxyquin molecules
Eurotiox ® , the most cost-effective antioxidant
Efficacy of synthetic antioxidants
Ethoxyqin 150
g/ton
60
Propyl gallate
100g/ton
40
25
BHT 200 g/ton
Days to reach 20
meq/kg peroxides
20
BHA 200 g/ton
0
10
20
30
40
50
60
Stability test in mixed fat - Dr. M. Coelho (1995)
Eurotiox ® , the most cost-effective antioxidant
70
Days
Formation of Ellagic Acid from Propyl
Gallate
Eurotiox ® , the most cost-effective antioxidant
Antioxidant Activity of BHA,
Propyl Gallate and Heterodimers
Compound
Antioxidant Activity
(t – t0)/(tBHA – t0)
Lard
Soybean Oil
(0.01%)
BHA
1.0
1.0
Propyl Gallate
1.50
12.25
Heterodimer A
0.88
4.0
HeterodimerB
0.91
1.50
T. Kurechi and A.Kunugi, J. American Oil Chem. Soc. 60:33 (1983)
Eurotiox ® , the most cost-effective antioxidant
Ethoxyquin/Propyl Gallate
SYNERGY mechanism
ETHOXYQUIN
H
N
CH3
CH3
CH2H5O
CH3
OXIDIZED ETHOXYQUIN
O
N
CH2H5O
CH3
Eurotiox ® , the most cost-effective antioxidant
oxidation point
CH3
Ethoxyquin/Propyl Gallate
SYNERGY mechanism
PROPYL GALLATE
COOCH2CH2CH3
O H
H O
O H
N
N
CH3
CH3
CH3
N
CH3
CH3
CH2H5O
CH3
CH2H5O
ETHOXYQUIN
Eurotiox ® , the most cost-effective antioxidant
CH3
CH3
CH3
Metal chelating
Effect of citric acid on soya oil stability
Peroxides (meq/kg)
300
250
200
150
100
50
0
CTR
Fe
Mn
Cu
No citric acid
46,6
293
85,4
288
with citric acid
10,7
125
13,1
44,4
Mustakas et Al. (1984)
Eurotiox ® , the most cost-effective antioxidant
Inhibition of Initiation by Chelation of
Copper
COO
CH2
O
CH2COOH
HOCCOOH
C
+
O
Cu++
HO
C
CH2
Cu+
+
CH2COOH
OOC
CH2
C
OH
O
C
CH2
COO
Citric Acid
Cu
Citrate complex with divalent cation,
forming two five-membered rings
Eurotiox ® , the most cost-effective antioxidant
O
COO
Eurotiox 32-Premix
Comparative granulometry
Eurotiox
Other
60
40
20
O ther
0
Eurotiox
0,05-0,13
0,13-0,22
0,34-0,46
0,46-0,67
0,67-1,10
1,10-1,67
>1,67
Eurotiox
50
42,4
6,2
0,6
0,4
0,2
0
Other
0,1
3,9
11
6,6
12,9
45,9
11,2
Particle size class ( Mesh, mm) - Sieve analysis by industrial lab, Belgium, July 1996
Eurotiox ® , the most cost-effective antioxidant
Two very
potent free
radical
scavengers
EUROTIOX unique antioxidant
complex
ETHOXYQUIN
- high purity (% mono)
Only
- high stability
proven
synergism
PROPYL GALLATE
-highly effective
- EtQ regenarator
+
Very
effective
economical
complex
CITRIC ACID
-metal scavenger
+
UNIQUE CARRIER
- high absorption
- free-flowing
- impr. stability
+
ALUMINIUM bag
-protected
Eurotiox ® , the most cost-effective antioxidant
stable
micropearled
Maximum
protection
at low
dosage
EUROTIOX ANTIOXIDANT
PROGRAM
Vitamins, Pigments
protection
in premixes & feed
Preventing
rancidity in
fat, oils, bone
meals
EUROTIOX
32-Premix
EUROTIOX
L-32
Eurotiox ® , the most cost-effective antioxidant
EUROTIOX
Dosage in feed and raw materials
Eurotiox ® , the most cost-effective antioxidant
EUROTIOX 32 Premix in feed



Eurotiox 32 Premix at 20 - 25 g/t in Feed with < 4% fat and < 1 month
storage time
+ 5 g/t for each 2% fat increase
+ 5 g/t for each month storage increase
Eurotiox ® , the most cost-effective antioxidant
EUROTIOX 32 Premix in feed
FAT LEVEL IN FEED
EUROTIOX 32 Premix
<4%
20 - 25 g/t
4 to 6 %
25 – 30 g/t
6 to 8 %
30 – 35 g/t
>8%
35 – 45 g/T
Eurotiox ® , the most cost-effective antioxidant
EUROTIOX 32 Premix in premixes
and concentrates

Vitamin premix: 50g/ton

Vitamin and traces premix: 100 g/ton

Vitamin and traces and choline chloride: 200 g/ton

Higher dosages are required in case proteins are present.
Eurotiox ® , the most cost-effective antioxidant
EUROTIOX L 32 for raw material
protection
Raw material
Vegetable oil
(crude)
Palm oil (crude)
Rice Bran oil
(crude)
Rice Bran oil
(Refined)
Sunflower oil
(crude)
Copra oil (crude)
Eurotiox L 32 dose Protection period
g/t
months
200
3
200
3
400
3
200
3
300
3
200
3
Soya oil (crude)
200 antioxidant
Eurotiox ® , the most cost-effective
3
EUROTIOX L 32 for raw material
protection
Raw material
Fish oil (crude)
Eurotiox L 32 dose
g/t
400
Protection period
months
3
Poultry fat
300
3
Lard
200
3
Tallow
100
3
Mixed fat
200
3
Squid oil
300
3
Used fat
500
2
Eurotiox ® , the most cost-effective antioxidant
Vitamin recovery test against oxidation
(Vitamin A in a vitamin mineral premix)
HPLC assay - 6 months testing period March ‘95-Sep ‘95
EUROTIOX 32-Premix - 45 g/ton
500
450
Vitamine A (gr)
400
350
45 g/t EUROTIOX 32
200, g/t ETQ-66%
300
250
200
150
Control
100
50
0
0
1
2
3
Months
Eurotiox ® , the most cost-effective antioxidant
4
5
6
Vitamin A Stability comparative test
Broiler feed - March 1997
EUROTIOX 32-Premix
8000
At 25 g/ton, EUROTIOX provides the best
VITAMIN A protection of all products
tested
Vit A (U.I./g)
7540
7500
7255
7295
7135
7000
7000
6500
Eurotiox
Pdt A
Pdt B
Pdt C
Pdt D
Project with large industrial company(Broiler integration) in Philippines. Vitamin detection
analysis performed by an independent laboratory (SERLABO) in the Netherlands.
Eurotiox ® , the most cost-effective antioxidant
Trial results
Eurotiox ® , the most cost-effective antioxidant
0
Tim e (h)
Eurotiox ® , the most cost-effective antioxidant
21
20,4
19,8
19,2
18,6
18
17,4
16,8
16,2
15,6
15
14,4
13,8
13,2
12,6
12
11,4
10,8
10,2
9,61
9,01
8,41
7,81
7,21
6,61
6,01
5,41
4,81
4,21
3,61
3,01
2,41
1,81
1,21
0,61
Pressure (bar)
EUROTIOX 32 PREMIX vs ENDOX
Feed, 7% fat
8
7
6
5
4
400 ppm ENDOX
80 ppm EUROTIOX 32 PREMIX
3
2
1
0
Eurotiox 32 Premix in meat and bone meal
(poultry origin)
 Trial
set-up:
– A control sample (no anti-oxydant added) and a treated
sample (150 ppm Eurotiox 32) was incubated in the
OXIPRESS.
– The OXIPRESS was running until the control sample was
completely oxidised.
– Both samples were analysed on their nutritional value and
compared to a control sample which was not put in the
OXIPRESS at all.
Eurotiox ® , the most cost-effective antioxidant
Eurotiox 32 Premix in meat and bone meal
(poultry origin)
CONTROL
WITHOUT
OXIPRESS
CONTROL WITH CONTROL WITH
OXIPRESS
OXIPRESS + 150
PPM EUROTIOX
32 PREMIX
Crude fat
(g/kg)
121.2
105.4
115.6
Metaboliseble
Energy
(MJ/kg)
11.13
10.22
10.95
Eurotiox ® , the most cost-effective antioxidant
Eurotiox 32 Premix in meat and bone meal
(poultry origin)
11,2
11
10,8
-1.6%
10,6
10,4
10,2
10
-8.1%
9,8
9,6
ME (poultry, MJ/kg)
Eurotiox ® , the most cost-effective antioxidant
Control
Control +
Oxipress
Control + oxipress
+ Eurotiox
OXIPRESS RESULTS
MBM oxypress 100°C
8
pressure (bar)
7
6
5
4
3
2
1
control
150 ppm EUROTIOX 32 Premix
0
0
5
10
15(h)
time
20
Eurotiox ® , the most cost-effective antioxidant
25
30
Eurotiox 32 Premix in meat and bone meal
(Poultry origin)
 Conclusions:
– Oxidation is responsible for loss of nutrients, mainly
energy
– EUROTIOX 32 PREMIX is able to prevent nutrient
losses due to oxidation.
Eurotiox ® , the most cost-effective antioxidant
Effect of EUROTIOX 32 PREMIX on energy
values (kcal/kg) of MBM (ruminant origin)
3600
3400
3200
Control
3000
27.5 ppm
EUROTIOX 32
PREMIX
2800
2600
2400
DAY 20
Source: Trial AO 002: INDIA
DAY 36
DAY 48
Eurotiox ® , the most cost-effective antioxidant
Eurotiox 32 Premix versus competitor in feed
(8% fat)
AR139 oxypress 100°C
8
Controle
7
25 ppm Eurotiox 32 premix
Competitor
pressure (bar)
6
5
4
3
2
1
0
0
5
10
15
time (h)
Eurotiox ® , the most cost-effective antioxidant
20
25