1. Food Chemicals: FATS triesters of glycerol with the fatty acids: hence triglycerides Fat or triglyceride glycerol fatty acids FATTY ACIDS (natural ones have even numbers of C’s, formed from acetyl-CoA = CH 3 CO--- CoA and are cis)

2. #C’S# DB'S POSITIONSNAMESOURCE 4/60 Butyric/caproicButter 8/100 Caprylic/capricCoconut 12/14/160Lauric/myristic/palmitic Palm 180StearicBeef fat 1819(-10)OleicOlive Oil 1829;12LinoleicSoy Bean 1839;12;15 LinolenicFish/Liver 200ArachidicPeanut 204 5;8;11;14 ArachidonicFish/Liver 220BehenicCanola (Rapeseed)

3. Systematic names: Butyric acid = butanoic acid4Cbutane Caproic acid = hexanoic acid6Chexane Capric acid = decanoic acid10Cdecane Lauric acid = dodecanoic acid 12Cdodecane Palmitic acid = hexadecanoic acid 16Chexadecane Stearic acid = octadecanoic acid18Coctadecane Arachidic= eicosanoic acid20C eicosane Behenic= docosanoic acid22Cdocosane DHA = docosahexaenoic acid 22C – 6 C=C (at 4,7,10,13,16,19 positions) - found in fish oils, membranes of eyes, brain

4. Linoleic acid is essential in our diets (we can make the others) Arachidonic acid: COX enzymes convert to prostaglandins, etc. Iodine # = g I 2 per 100g of oil (a measure of unsaturation) OIL% SATD% MONO% POLY IODINE # Coconut93618-10 Butter25-40 Palm5736737-54 Lard44461045-70 Margarine80-85 Olive15731275-95 Peanut21493085-100 CANOLA76132~115 Cottonseed262252100-117 Corn142957115-130 Fish120-180 Soybean142462125-140 Safflower101476130-140 Sunflower111970130-145 Linseed170-205

5. All natural fatty acids are all cis: but can be isomerized to trans trans-isomers are higher melting than cis-isomers: solid fats vs. oils Saturated fats (no double bonds): pack better, higher Mp = SOLIDS

6. Can increase mp of OIL by HYDROGENATION and/or ISOMERIZATION to get solids = margarine The more double bonds, THE HIGHER THE IODINE NUMBER a) BUTTER has IN=30, mostly C4-C6-C8 short chain saturated acids: IN varies with the milk source (diet of the cow) b) SOYA OIL has IN=120-140, mostly C18 with 2-3 double bonds: part hydrogenated, part isomerized to get Margarine, IN ~85 (NOTE: olive oil also has IN=90, but is all cis and thus is an OIL) CANOLA OIL used to be mostly C22 but selective plant breeding has produced modern Canola strains that are mostly C18: 7% satd; 61% mono unsaturated; 32% polyunsaturated Now mostly (91%) C18: C18-1 = Oleic (55%) C18-2 = Linoleic (26%) C18-3 = Linolenic (10%) so 0.91 x 26% = 21% Linoleic in Canola

7.  -6 and  -3 oils  -6 FATTY ACID  -Linolenic acid Plant Oils  FATTY ACID  Linolenic acidFish oils Modern diets are high in  -6, about 10x the  -3, while old diets were about 1:1

8. Current theory is that  -3 gives lower blood triglyceride levels PLUS 1g of  -3 per day has been shown to give a 20% reduction in heart-related deaths Lack of  -3 leads to heart disease, thrombosis, atherosclerosis Modern Canola has about 11%  -3 while decreasing Erucic acid C22-1(13-14) to <1% Erucic acid was prevalent in old rapeseed oil and has been implicated in heart lesions As a matter of interest see: Monsanto vs. Schmeiser – a well-documented court case where Monsanto sued Schmeiser for patent infringement when he saved seeds from a Round-up Ready (a genetically modified Canola strain) Canola that had blown into his field from neighbouring areas

9. Trans-fats (US and CAN require labelling) Modern margarine has some cis-bonds isomerized to trans to increase ‘solidity’: Hard margarine ~12% trans-fats Soft margarine ~5% trans-fats Becel 0% trans-fat but still ~12% saturated fat Current hypothesis: trans fats increase LDL’s a few % = a small increase in risk of heart attack Ban on use of trans-fats in restaurants comes into effect in BC in September ’09 (already adopted, then abandoned in Calgary)

10. DISADVANTAGES of unsaturated fats: easier to oxidise -CH=CH-CH-CH=CH- | H Allylic hydrogen is easily oxidised to a free radical which further reacts with oxygen to cleave the chain and produce SMELLY short chain fatty acids (under-arm sweat and rancid butter smell) An ANTIOXIDANT (usually ArOH) can supply a H back to this free radical and reform the fat, before it has had time to react with oxygen: the resulting phenoxy radical ArO is stable. NOTE: Butylated hydroxytoluene (BHT) is 2-t-butyl-4-methylphenol and it is commonly added to cereals for the same reasons (next page)

11. Hence need to protect fats with antioxidants: BHT BHA VITAMIN E butylated- butylated-  -tocopherol hydroxytoluene hydroxyanisole allowed at 0.01-0.02% too expensive for food Note: in these the ArO is highly crowded which makes it less reactive

12. FLAVINOIDS eg. epicatechin are found in green and black teas, red wines and also have antioxidant properties: reduced heart disease? ANTHOCYANINS R2, R5, R7 virtually always OH and other R groups may be OH Powerful anti-oxidants found as pigments in berries, flowers, vegetables, outer skins: blueberries, blood oranges, jalapeno peppers, purple onions, red apple skins, many others

13. OILS: Vegetable oil production 80-100 Mtons/y mostly as Soy, Palm, Canola (about ~20% each) plus minor amounts of coconut and peanut oils Soft margarine has 80% fat 16% water Low fat soft margarine has 40%fat 56% water!!! Fats don’t dissolve in water, so have to emulsify them A piece of dirt (grease): hydrocarbon tails embed in grease; water surrounds the - COO - groups and the grease ‘dissolves’”

14. For fats can use phospholipids: eg. Lethicin (egg yolks) C 17 H 31 COO-CH 2 | C 17 H 31 COO-CH | - + CH 2 OPO 3 CH 2 CH 2 NMe 3 greasy end binds fationic end binds water Remember bile acids transport fats thru the intestine for use Cholic acid:

15. Similarly mono- or diglycerides bind fats to sugars: C 17 H 31 COO-CH 2 | CH-OH | CH 2 -OH greasy end binds fat this H-bonds to sugar -OH’s so used in shortenings, cakes and cookies: can get up to 40% sugar in a cake without it being ‘crunchy’; fats make cookies more ‘crumbly’

16. FAT SUBSTITUTES Some are ‘modified’ starches, have the texture of fat but 4 kcal/g rather than 9 kcal/g OLESTRA each -OH of sucrose is converted to a -OCO(CH 2 ) 6,7,8 CH 3 the resulting molecule cannot pass through the intestine, so is not absorbed: because it is so ‘greasy’ it can lubricate the intestines too much so ‘anal leakage’ can occur carrying with it some fat soluble vitamins

17. Natural Waxes are long chain acid / long chain alcohol esters: CH 3 (CH 2 ) 24/26 COO(CH 2 ) 29/31 CH 3 = beeswax Carnauba wax (used for car polish and coatings on ‘no-mess’ candies like Smarties, M+M’s) contains some pendant HO~~~~COOH that polymerize and give it its hardness CANNOT DIGEST THESE Jojoba oil is an unsaturated ‘wax’ that is not metabolised: under study as a frying oil CH 3 (CH 2 ) 7 CH=CH(CH 2 ) m COO(CH 2 ) n CH=CH(CH 2 ) 7 CH 3 m = 9,11; n=10,12 chain lengths vary Used in cosmetics as a moisturizer and in many skin and hair care products; also under investigation as a diesel oil

18. Cholesterol, Fats and Oils, Salt and Calories in Foods (per 100g) Food Cholesterol Oil or Fat (grams)SaltCal mgSatur Mono-un Poly-unmg Beef, raw912.72.70.554152 Chicken851.31.51.070165 Cheese (cheddar)10521.19.40.9615400 Corn oil012.724.258.70884 Eggs, whole5483.44.51.4142143 Hot dog, all beef5112.714.81.21026296 Milk, whole142.31.10.14060 Olive oil013.573.78.40884 Margarine (Becel)010.030.040.0700700 Butter21550.523.43.0576720 Tuna (canned)630.20.10.2338116 Salmon (canned)351.01.82.7487140 Peanut butter (unsalted)09.723.315.217*588 Yogurt (plain, skim milk)61.00.40.047756