SEAL BLUBBER OIL, SEAL BLUBBER OIL, SPECIALTY LIPIDS AND SPECIALTY LIPIDS AND OMEGA-3 FATTY ACIDS OMEGA-3 FATTY ACIDS

Department of BiochemistryDepartment of Biochemistry

Memorial University of NewfoundlandMemorial University of Newfoundland

St. John’s, NL, A1B 3X9, CanadaSt. John’s, NL, A1B 3X9, Canada

MI and Dietary Fat Intake of MI and Dietary Fat Intake of Eskimos versus DanesEskimos versus Danes

Eskimos Eskimos DanesDanes

Myocardial Infarction 3 40Myocardial Infarction 3 40

Energy from fat (%) 39 42Energy from fat (%) 39 42

n-6 PUFA (g/d) 5 10n-6 PUFA (g/d) 5 10

n-3 PUFA (g/d) 14 3n-3 PUFA (g/d) 14 3

n-3/n-6 2.8 0.3n-3/n-6 2.8 0.3

Cholesterol (mg/d) 790 420Cholesterol (mg/d) 790 420

Coronary Heart Disease (CHD)Coronary Heart Disease (CHD)

There are 3 stages in the development of CHD:There are 3 stages in the development of CHD: Injury to the coronary artery wall;Injury to the coronary artery wall; Build up of a fatty a fibrous plaqueBuild up of a fatty a fibrous plaque (atherosclerosis);(atherosclerosis); Formation of a blood clot (thrombosis);Formation of a blood clot (thrombosis); If a clot forms in an artery which is already If a clot forms in an artery which is already

narrowed by atherosclerosis, a heart attack narrowed by atherosclerosis, a heart attack can occurcan occur

Omega-3 fatty acids may have Omega-3 fatty acids may have positive effects on:positive effects on:

High blood pressureHigh blood pressure Body TAG and Body TAG and

cholesterolcholesterol Abnormal blood clotting Abnormal blood clotting

(thrombosis)(thrombosis) Fat deposition Fat deposition

(atherosclerosis)(atherosclerosis) Cardiovascular diseasesCardiovascular diseases

Other Effects of Marine OilsOther Effects of Marine Oils

Relieve arthritisRelieve arthritis Improve diabetic conditionImprove diabetic condition Enhance body immunityEnhance body immunity

Thinning of bloodThinning of blood Diarrhea and nausea in certain Diarrhea and nausea in certain

conditionsconditions

Breast Feeding and Intellectual Performance

Weschler Intelligence Group I Group II

scale for children No mother’s Mother’s milk Δ1

milk

Verbal scale 92 102 8.9*

Performance scale 93 102 8.1*

Overall IQ 93 103 8.3*

* p<0.0001

Reference: Lucas et al. 1992

EPA (C20:5)

DHA (C22:6)

DPA (C22:5)

CH2 O C

O

Sn-1

HO CH

CH2 O C

O

Sn-3

R1

R3

Sn-2

CH2 O C

O

C O CH

CH2 O C

O

Sn-3

Sn-1O R1

R3

R2

Fatty Acid Composition of Seal Blubber, Fatty Acid Composition of Seal Blubber, Menhaden and Algal OilsMenhaden and Algal Oils

Fatty acid Seal BlubberFatty acid Seal Blubberaa Menhaden Algal Menhaden Algal

10:0 10:0 - - - - 1.21.212:0 12:0 - - - - 6.06.014:014:0 3.4(4.3) 3.4(4.3) 8.38.3 16.8 16.814:114:1 1.0(1.2) 1.0(1.2) 0.40.4 - -16:016:0 5.0(7.9) 5.0(7.9) 17.1 17.1 14.0 14.016:1n-716:1n-7 15.1(22.0) 15.1(22.0) 11.4 11.4 1.51.518:1n-9 & n-1118:1n-9 & n-11 26.4(22.4) 26.4(22.4) 12.1 12.1 14.7 14.718:2 n-618:2 n-6 1.3(1.6) 1.3(1.6) 1.41.4 0.50.520:1 n-920:1 n-9 15.0(8.8) 15.0(8.8) 1.41.4 --20:5 n-320:5 n-3 5.4(9.7) 5.4(9.7) 13.2 13.2 0.10.122:1 n-1122:1 n-11 3.6(1.7) 3.6(1.7) 0.10.1 --22:5 n-322:5 n-3 4.9(5.8) 4.9(5.8) 2.42.4 --22:6 n-322:6 n-3 7.9(9.9) 7.9(9.9) 10.1 10.1 43.5 43.5

aa Values in parentheses are for ringed seal blubber oil Values in parentheses are for ringed seal blubber oil

1

23

2 + FFAs

A

Pancreatic lipase

B

CH3Mg Br

1

2OH

OH

23

Tertiary alcoholMAGs+ + + + 1

HO

3

c

1

2P

P

23

+ D

Dichlorophenylphosphate + H2O

Phospholipase A2

1

HO

P

P

23

+ + FFAsPancreatic lipase P

2

OH+ FFAs

F G

E H

TAGs

STEREOSPECIFIC ANALYSES

Instability of Omega-3 OilsInstability of Omega-3 Oils

• Oxidation results in: - Loss of EPA% and DHA% - Off fishy odor and/or taste

• Prone to oxidation primary secondary

EPA/DHA peroxides aldehydes ketones, etc

Indicators: Peroxide p-Anisidine Value Value

• Oxidation results in: - Loss of EPA% and DHA% - Off fishy odor and/or taste

Stability and Stabilization of Stability and Stabilization of Edible OilsEdible Oils

Stability of edible oils depends on:Stability of edible oils depends on: Degree of unsaturationDegree of unsaturation Position in the triacylglycerol moleculePosition in the triacylglycerol molecule Minor componentsMinor components Process/ storage conditionsProcess/ storage conditions

C

O OH

R2R1

H

C

O •

R2R1

H

+ • OH

C HR1

O

+ R2 •

+ RH C R1

O

+ ROHR2

C

OH

R2R1

H

+ R •

Lipid hydroperoxide Alkoxy radical Hydroxyl radical

Aldehyde

Alcohol

Ketone Ketone Alcohol

RHRO

•

R •

C R1

O

R2

DOUBLE BOND INDEX (DBI)

• DBI = 1 x (% monoenes / 100) + 2 x (% dienes / 100) + 3 x (% trienes / 100) + ……… etc.

• DBI = mean number of double bonds per fatty acid

METHYLENE BRIDGE INDEX (MBI)

• MBI = mean number of bis-allylic methylene bridge positions per fatty acid

• MBI = 1 x (% dienes / 100) + 2 x (% trienes / 100) + … etc.

Fatty acida BOb Modified BO EPO Modified EPO

16:018:018:118:2618:3620:120:5322:122:63

9.8 (0.1) 3.1 (0.3)15.2 (0.7)38.4 (0.9)24.4 (0.9) 4.1 (0.3) NDc

2.5 (0.1) NDc

5.1 (0.4) 2.1 (0.1)10.7 (0.1)22.5 (0.3)17.4 (0.2) 2.6 (0.1)25.9 (0.5) 1.7 (0.3) 9.6 (0.8)

6.2 (0.1) 1.7 (0.1) 8.7 (0.6)73.6 (0.9) 9.1 (0.4) NDc

NDc

NDc

NDc

3.4 (0.1) 1.0 (0.1) 6.1 (0.1)45.9 (0.2) 7.6 (0.1) 0.2 (0.1)25.7 (0.6) NDc

7.9 (0.1)

Fatty acid profile of borage (BO) and evening primrose oils (EPO)before and after enzymatic modification by Pseudomonas sp.

aw/w%; bMean (SD); cNot detected

3/6 ratio DBI MBI

0.902.992.09

0.632.972.03

-1.720.87

-1.830.92

Tocopherols (mg/kg)

BOa Modified BO EPO Modified EPO

Total

- 116 (0.8)

1116 (1.5)

1232

- -

483 (0.9)

483

112 (0.7) 202 (0.2)

56 (0.9)

370

99 (0.1) 122 (0.2)

52 (0.8)

273

Tocopherol content of borage (BO) and evening primrose oils (EPO) before and after enzymatic modification

aMean (SD)