PART 2

FOOD ADDITIVES CONTRIBUTING TO IMPROVE

THE SHELF-LIFE
Chương 5: ANTIOXIDANTS
Group 4: Antioxidant
A food additive, which prolongs the shelf-life of foods by protecting against
deterioration caused by oxidation.

▪ antibrowning agent
▪ antioxidant
▪ antioxidant synergist
 1. Các chất chống nâu hóa

Nâu hóa là vấn đề

• Thực phẩm nguồn gốc thực vật có thể bị biến đổi hóa học
trong quá trình:
➢sau thu hoạch,
➢chế biến,
➢hoặc lưu trữ,
Các phản ứng biến đổi màu (nâu hóa) được chia thành 2 loại:
1. Nâu hóa do enzyme
2. Nâu hóa không do enzyme.
Ví dụ:
- Nâu hóa trong quá trình cắt rau quả tươi và tiếp xúc không khí?
- Nâu hóa trong quá trình thanh trùng nước quả?
Nâu hóa do enzyme là kết quả của:
- Oxy hóa các hợp chất polyphenols chuyển thành quinones,
- Được xúc tác bởi các enzyme polyphenol oxidase:
• PPO
• Tyrosinasa
• o-diphenol oxidase
• catechol oxidase
- Các phản ứng tiếp tục diễn ra và polymer hóa các quinones.
Kiểm soát nâu hóa do enzyme:
1. Sử dụng phương pháp chần,
2. Acid hóa; ứng dụng sulfites
3. or sử dụng các chất thay thế sulfites như:
– ascorbic acid
– cysteine.
Các chất thay thế này hiệu quả kém hơn so với sulfites
Chemistry of browning reactions in foods
Chemistry of browning reactions in foods
• The optimum pH for PPO activity is between 5 and 7
• PPO is relatively heat liable
• and PPO-catalyzed reactions can be inhibited by:
➢acids
➢phenolic acids,
➢sulfites
➢ascorbic acid
 Sulfites
• Sulfite may be applied as:
➢ E220 Sulphur dioxide
➢ E221 Sodium sulphite
➢ E222 Sodium bisulphite,
➢ E223 Sodium metabisulphite
➢ E224 Potassium metabisulphite
➢ E225 Potassium sulphite
➢ E226 Calcium sulphite
➢ E227 Calcium hydrogen sulphite,
➢ E228 Potassium bisulphite
• Sulfite có nhiều dạng tồn tại ở dạng nào tùy thuộc vào bản
chất của thực phẩm
• Do đó nhiều chất tương đồng của sulfite được phát triển để
giải quyết vấn đề công nghệ.
➢E220 (sulphur dioxide) được sử dụng xử lý xông quả chống
hóa nâu. Ngoài ra nó cũng có thể sử dụng điều chỉnh độ acid và
chất bảo quản vi sinh
➢E223 và E224 đặc biệt rất bền khi lưu trữ do đó sử dụng trong các
kho bảo quản là phù hợp.
➢E226 rất tan ít trong nước nên sử dụng được khi yếu tố hòa tan
không phải ưu tiên hàng đầu
 Quá trình oxy hóa (oxidation)
• Oxidation là một phản ứng hóa học chuyển các electron hoặc
hydrogen từ một cơ chất sang chất oxy hóa.
• Phản ứng oxy hóa tạo ra các gốc tự do (free radicals). Sau đó,
các gốc tự do này sẽ tạo ra phản ứng oxy hóa dây chuyền.
 Oxidation

Oxy hóa làm biến đổi thực phẩm:

➢ôi hóa (rancidity),

➢mất mùi vị,
➢mất màu sắc
➢mất giá trị dinh dưỡng.
 Oxidation

Mức độ oxy hóa phụ thuộc vào:

1. Tồn tại các chất oxy hóa tự nhiên trong thực phẩm,
2. Có mặt của oxy,
3. độ nhạy của cơ chất đối với phản ứng oxy hóa,
4. nhiệt độ và ánh sáng,
 ANTIOXIDANTS
STABLISED RADICALS
AA NON RADICALS
ANTIOXIDANTS AH A• AX

ROO• ROOH
PEROXIDE AND R• RH
FREE RADICALS RO• ROH

Ascorbic Acid
Propyl Gallate
Ascorbyl Palmitate
Tertiary Butylhydroquinone
Ascorbyl Stearate
Guaiac Resin
Calcium Ascorbate
Butylated Hydroxyanisole
Mixed Tocopherols Concentrate
Butylated Hydroxytoluene
Tocopherol, Alpha-
 ANTIOXIDANTS
• Ascorbic acid, tocopherols, gallic acid, BHA and BHT
• Often a combination of two or more antioxidants is more
effective than any one used simply because of their synergistic
effects.
• The presence of other agents, such as citric acid, may also have
a synergistic effect, by reducing the availability of metallic ions
that may catalyse oxidation reactions.
.
 ANTIOXIDANTS
• The use of the powerful synthetic antioxidants BHA, BHT and the gallic
acid is very restricted.
• Tocopherols, which can be either natural or synthetic, are less restricted
but are less effective in the protection of processed foods.
• Antioxidants cannot restore oxidized food; they can only retard the
oxidation process.
• The most effective use of antioxidants is therefore in the fats and oils
used in the manufacturing process.
 ANTIOXIDANTS

SAFE

Low concentration required (0.01-

0.02%)
ANTIOXIDANTS Distribute at interfaces
→ Highly hydrophobic
→ In contact with air

Stable in processing conditions

• Regulated differently country by country
• Many antioxidant but few approved by:
Joint FAO/WHO Expert Committee on Food Additives (JECFA)
European Community’s Scientific Committee for Food (SCF)
 ADI (mg/kg bw)
propyl gallate 0–2.5
BHA 0–0.5
BHT 0–0.125
TBHQ 0–0.2
tocopherols 0.15–2.0
gum guaiac 0–2.5
ethoxyquin 0–0.06
phosphates 0–70.0
EDTA 2.5
tartaric acid 0–30.0
citric acid not limited
lecithin not limited
ascorbic acid not limited
sulphites (as sulphur dioxide) 0–0.7
ascorbyl palmitate or ascorbyl 0–1.25
stearate (or the sum of both)
 ASCORBIC ACID H2C–OH

INS 300 H – C – OH O
O
Chemical names: L-Ascorbic acid, ascorbic acid, 2,3-didehydro-L-
threo-hexono-1,4-lactone, 3-keto-L-gulofuranolactone H

DESCRIPTION: White to slightly yellow, odourless crystalline

OH OH
powder; melting point about 190oC with decomposition

SOLUBILITY: Freely soluble in water; sparingly soluble in ethanol; insoluble in ether

LOSS ON DRYING

pH : 2.4 - 2.8

MAX LEVEL: GMP (In accordance with good manufacturing practices; or sufficient for purpose;
or quantity not greater than required)

ADI: for ascorbic acid and its Ca, K and Na salts, of 0-15 mg/kg
 Ascorbic acid + palmitic acid = Ascorbyl palmitate (Vit C ester)
E305
Chemical names:
▪ Ascorbyl stearate;
O
▪ L-ascorbyl stearate;
H2C–O–C–(CH2)16 – CH3
▪ 2,3-didehydro-L-threo-hexono-1,4-lactone-6-stearate;
▪ 6-stearoyl-3-keto-L-gulofuranolactone H – C – OH O
Chemical formula: C24H42O7 O

Description: White or yellowish-white solid, with a citrus-like

H
odour
Functional use: Antioxidant
OH OH

Solubility: Very slightly soluble in water; freely soluble in

ethanol
Melting range: 107 o - 117o
Max level: 5.000mg/Kg
ADI: 0 – 1,25 mg/Kg
 Ascorbic acid + stearic acid = Ascorbyl stearate (Vit C ester)
E304

Chemical names: O
▪ Ascorbyl palmitate; H2C–O–C–(CH2)14 – CH3
▪ L-ascorbyl palmitate; H – C – OH O
▪ 2,3-didehydro-L-threo-hexono-1,4-lactone-6-palmitate;
O
▪ 6-palmitoyl-3-keto-L-gulofuranolactone
H
Chemical formula : C22H38O7
Description : White or yellowish-white solid, with a citrus-like odour
Functional use : Antioxidant OH OH

Solubility : Very slightly soluble in water; soluble in ethanol

Melting point : 116o

Max level : 5.000mg/Kg

ADI : 0 – 1,25mg/Kg
 E310 Propyl gallate, E311 Octyl gallate,
E312 Dodecyl gallate

They are fat-soluble and are added to fats and oils to delay or
prevent rancidity
 E310 Propyl gallate, E311 Octyl gallate,
E312 Dodecyl gallate
Benefits
• Propyl gallate is synergistic with other antioxidants, such as BHA and BHT.
• It is particularly effective with polyunsaturated fats.
• The antioxidant activity is maintained when the fat is blended with other
ingredients in a final foodstuff.
• The longer chain length of the octyl and dodecyl gallates gives advantages
over propyl gallate in terms of:
➢ greater solubility in fats
➢ and greater stability.
 E310 Propyl gallate, E311 Octyl gallate,
E312 Dodecyl gallate

Limitations
The gallates are fat-soluble, but need to be dissolved in a small quantity of hot
fat first before being diluted with the rest of the fat
 BUTYLATED HYDROXYANISOLE (BHA)
OH
ISN 320 OH
C(CH3)3

C(CH3)3
O–CH3 O–CH3

Chemical names : 3-Tertiary-butyl-4-hydroxyanisole, a mixture of 3- and 2-tertiary-

butyl-4-hydroxyanisole

DESCRIPTION : White or slightly yellow crystals or waxy solid, with a faint characteristic
odour

SOLUBILITY : Insoluble in water; freely soluble in ethanol and propane-1,2-diol

MAX LEVEL : 200mg/Kg

ADI : 0 – 0,5 mg/Kg

 BUTYLATED HYDROXYANISOLE (BHA)
ISN 320

Function in Food
• Butylated hydroxyanisole is an antioxidant and is added to delay or
prevent rancidity in fats and oils in foodstuffs.
• It is insoluble in water and is best suitable to foods with a high fat
content.
• BHA is often used in combination with other antioxidants such as BHT
to give a synergistic effect.
 BUTYLATED HYDROXYANISOLE (BHA)
ISN 320

Benefits
BHA is stable to heat and mildly alkaline conditions,
giving it a property that makes BHA particularly
suitable in baked and fried foods
Limitations
BHA is a very effective antioxidant for animal fats, but
its effect is less marked in vegetable oils that are
being stored at ambient temperatures.
 BUTYLATED HYDROXYTOLUENE (BHT)
ISN
OH
321
(H3C)3C C(CH3)3

O–CH3

Chemical names: 2,6-Ditertiary-butyl-p-cresol, 4-methyl-2,6-ditertiary-butyl-phenol

DESCRIPTION: White, crystalline or flaked solid, odourless or having a characteristic faint aromatic
odour

SOLUBILITY: Insoluble in water and propane-1,2-diol; freely soluble in ethanol

MELTING POINT: 69 – 72oC

MAX LEVEL: 100mg/Kg

ADI: 0 – 0,3 mg/Kg

 BUTYLATED HYDROXYTOLUENE (BHT)
ISN 321

Function in Food
• Butylated hydroxytoluene is an antioxidant and is added to delay
or prevent rancidity in fats and oils in foodstuffs.
• It is insoluble in water and is best suitable to foods with a high fat
content.
• BHT is often used in combination with other antioxidants, such as
BHA, to give a synergistic effect.
 BUTYLATED HYDROXYTOLUENE (BHT)
ISN 321

Limitations
BHT is more steam-volatile than BHA, and this makes it unsuitable
for use on its own in frying oils, particularly where high-moisture
foods are being fried.
 ANTIOXIDANT
Chelating agent (sequestrant)

STABLILSED COMPLEX

METAL IONS

EDTA (Ethylene Diamine Tetra Acetate)

Calcium Disodium Ethylene Diamine Tetra Acetate
Disodium Ethylene Diamine Tetra Acetate
Polyphosphates
Ortho- , Pyro-phosphoric acid
Isopropyl citrate
 CALCIUM DISODIUM ETHYLENE DIAMINE TETRA ACETATE
–
INS CH
385–COO–
OOC–H2C 2
NCH2CH2N 2Na+ , Ca++
–OOC–H
2C
CH2–COO–

SYNONYMS : Calcium disodium EDTA

Chemical names: N,N'-1,2-Ethanediylbis[N-(carboxymethyl)-glycinate](4-)-N,N',O,O',ON,ON]calciate(2-)
disodium; Calcium disodium ethylenediaminetetraacetate; Calcium disodium (ethylene-dinitrilo)-
tetraacetate.
DESCRIPTION: White, odourless crystalline granules or a white to nearly white powder; slightly
hygroscopic
FUNCTIONAL USES : Sequestrant, preservative

SOLUBILITY: Freely soluble in water, practically insoluble in ethanol.

pH : 6.5 - 7.5

MAX LEVEL : beverages : 25 – 35mg/Kg, fish : 50, fruits vegetables products 100 – 200, dried vegetables
600 – 800

ADI : 0-2.5 mg/kg

 DISODIUM ETHYLENE DIAMINE TETRA ACETATE
INS 386
–OOC–H C
2
CH2–COO–
NCH2CH2N 2Na+
–OOC–H
2C
CH2–COO–

SYNONYMS : Disodium EDTA, disodium edetate

Chemical names : Disodium salt of N,N'-1,2-Ethanediylbis[N-(carboxymethyl)glycine];
disodium dihydrogen ethylenediaminetetraacetate; disodium dihydrogen (ethylene-
dinitrilo)-tetraacetate
DESCRIPTION: White, odourless crystalline granules or a white to nearly white powder
FUNCTIONAL USES : Sequestrant, antioxidant synergist, preservative
SOLUBILITY : Freely soluble in water, practically insoluble in ethanol.
pH : 4.3 – 4.7
MAX LEVEL : beverages : 25 – 35mg/Kg, fish : 50, fruits vegetables products 100 – 200,
dried vegetables 600 – 800

ADI : 0-2.5 mg/kg

 SODIUM POLYPHOSPHATES
INS 452
O– O– O–

O P O– O P O– O P O–

O O
O
O P O– O P O–
O P O–
O– O n
O P O–
O
O– O P O–

O–
 SODIUM POLYPHOSPHATES
INS 452

pH changing from 3-9

Chemical names : Sodium tetrapolyphosphate, sodium hexametaphosphate,

sodium polyphosphate

DESCRIPTION : Colourless or white, transparent platelets, granules, or powders

FUNCTIONAL USES : Emulsifier, sequestrant, texturizer

SOLUBILITY : Very soluble in water

MAX LEVEL : 0.6 – 1.0 %

MTDI (Maximum Tolerable Daily Intake): 70 mg/kg

 O O O
PENTASODIUM TRIPHOSPHATE NaO P O P O P ONa
INS 451 NaO NaO NaO

SYNONYMS : Pentasodium tripolyphosphate, Sodium triphosphate, Sodium tripolyphosphate,

Triphosphate

Chemical names : Pentasodium triphosphate, pentasodium tripolyphosphate

DESCRIPTION : White, slightly hygroscopic granules or powder

FUNCTIONAL USES: Sequestrant, texturizer

SOLUBILITY : Freely soluble in water; insoluble in ethanol

pH : 9.1 - 10.1

MAX LEVEL : 0.6 – 1.0 %

No ADI was established, MTDI : 70 mg/kg

 ISOPROPYL CITRATE
CH2 – COOR
INS 384
HO CH COOR R isopropyl or hydrogen

CH2 – COOR

Chemical names : Citric acid mixed ester of 2-propanol.

FUNCTIONAL USES : Antioxidant, sequestrant

SOLUBILITY : Soluble in water and ethanol

MAX LEVEL : 200mg/Kg

ADI : 0-14 mg/kg

 Antioxidative factor (AF) = IA/I0

AF values of some antioxidants (0.02%) in refined lard

Antioxidant AF Antioxidant AF

d--tocopherol 5
Octyl gallate 6
d--tocopherol 12
Ascorbyl palmitate 4
BHA 9.5
BHA+BHT (0.01%+0.01%) 12
BHT 6
AH được gọi là gì?

A. Chất liên kết kim loại B. Chất làm ngọt

C. Chất chống oxy hóa D. Chất tạo nhũ tương
Chất X được gọi là gì?
A. Chất liên kết kim loại B. Chất làm ngọt
C. Chất chống oxy hóa D. Chất tạo nhũ tương
Cho sản phẩm như bên dưới, dựa vào phân tích của bạn, chất phụ gia 320 và 321 được sử dụng
chủ yếu để bảo vệ thành phần nào tránh bị oxy hóa?
A. Protein B. Curcumin
C. Dầu thực vật D. Bột mì
Để chống oxy hóa cho sản phẩm chứa 50% dầu và 30% nước, ta nên sử dụng loại phụ gia nào?
A. BHA B. BHT
C. Vitamin C D. Ascorbyl stearate