Lecture Five Lipids -Organic compounds (CnHnOn) that contains more C and H in proportion to O than does CH2O -Insoluble in water, but soluble in organic solvents (ether, acetone, benzene) -Supplies 40% of the calories in American diets -Source of essential fatty acid -Necessary for fat soluble vitamins A, D, K and E -Concentrated form of energy -1g of fat = 9.45kCal -1g of protein or CH2O = 4.1 kCal -On average 2.25 times more energy in fat than CH2O or protein -Important for hibernating animals -Simple Lipids -Esters of fatty acids and alcohol (glycerol) -Fats and oils = esters of fatty acids and glycerol -Waxes = esters of fatty acids and alcohol (not glycerol) -Compound Lipids -Esters of fatty acids, also containing nonlipid substances (P, CH2O, proteins) -Phospholipids (phosphoric acid, N) membranes, transport/emulsification -Glycolipids (CH2O, N) -Lipoproteins carriers in blood and tissues (LDL, HDL, VHDL) -Derived Lipids -Substances derived from simple and compound lipids by hydrolysis -Sterols -Lipids with complex phenanthrene type ring structure -Terpenes -Isoprene type structures -Structure of Lipids -Fatty Acids -Carbon chains from 2-24 in length -Even numbered straight chained in most animal tissue -Some branched in ruminants -Carboxyl group at the end of each -RCOOH general structure (R stands for fatty acid chain) -CH3CH2COOH is acetate -Double bond vs. H Saturation -Stearic C18:0 number of double bonds -Linolenic C18:3 number of double bonds -Isomers -Cis -Trans (margarine, other hydrogenated fats) -Glycerol is an alcohol -Mono, Di, and triglycerides are esters of fatty acids and glycerol -Mono, Di, and triglycerides -Typically are mixed triglycerides (98%) -Chain length, degree of saturation determines physical properties -TG of C10:0 or longer = solid at room temperature -TG of less than C10 = liquid at room temperature -TG with each fatty acid saturated = solid -TG with more unsaturated fatty acids = liquid -Fats can have 10 or more different fatty acids -Lipids -Phosopholipids -Usually contain fatty acids (hydrophobic), phosphoric acid (hydrophilic), a glycerol, a nitrogenous base -Higher in unsaturated fatty acids than lipids in adipose tissue -Widely dispersed in body fluids -Emulsifying properties that help to function in lipid transport -Sterols -Phenanthrene type ring -Cholesterol, ergosterol, 7-dehydrocholesterol, androgens, estrogens, progesterone -Lipid Functions -Energy supply -2.25 times that of CH2O and protein -Source of essential fatty acids (EFA) -Can not be synthesized in adequate amounts -Linoleic Acid (C18:2) and linolenic acid (C18:3) -Arachidonic acid (C20:4) can be synthesized from linoleic acid -Involved in maintenance of skin integrity in nonruminants -Young ruminants require essential fatty acids in diet (just like non ruminants) -Carriers of fat soluble vitamins -Vitamins A, D, E and K -Absorption is a function of digestion and absorption of fats -Mixed micelles containing monoglycerides and FFA’s higher rate of vitamin uptake -Source as insulation and protection as well as heat generation -Lipid Absorption -Site of major fat processing—upper small intestine -Fats (mostly triglycerides) mix with bile and pancreatic and intestinal secretions -Bile salts act as emulsification agents (detergent like action) -Particle size decreases increasing surface area and exposure to lipases -Lipases attach fatty acid in 1 and 3 positions result in beta monogylcerides and free fatty acids -Monoglycerides + FFA + bile salts + phospholipids + cholesterol=mixed micelles -Bile Salts -Secreted in large quantities, reabsorbed in jejunem and ileum, recycled in liver -Facilitate digestion and absorption of lipids -Absorption of fat soluble vitamins -Cholesterol absorption -Mixed micelles combine with cholesterol and fat soluble vitamins = larger mixed micelles -Main site of absorption is upper jejunem, some absorption in duodenum and ileum -Upon entering mucosal cell -Fats are reassembled into triglycerides -Protein coating takes place to form chylomicrons (triglycerides, phospholipids, cholesterol, esters, and protein) -Chylomicrons enter lacteals via intercellular space lymphatic system thoracic duct -Mammals absorb long chain fatty acid lipids via lymph (chickens absorb directly into portal blood) -Transport of Lipids -Blood lipids -Chylomicrons -Lipids arising from mobilized depot stores -Lipids synthesized in body tissues (liver and adipose) -Transported as lipoproteins -4 Major Classes -Chylomicrons (highest ratio of lipids to proteins) -VLDL (very low density by lipoproteins) -LDL -HDL -Lipid Deposition -All tissues store triglycerides -Adipose tissues are most significant sites -Can synthesize TG from CH2O and oxidize fats -TG are ready source of energy so, there is continous triglyceride deposition and mobilization -Energy intake in excess results in net deposition of TG. Reverse is also true -Fat depot=fatty acid characteristics for each animal -Non ruminants= dietary fatty acid influences fat depot -Ruminants= less responsive, bypass fats -Fatty Acid and TG to Metabolism -Major sites of lipid metabolism -Liver -Mammary gland -Adipose tissue -Liver (example) -Synthesis of : -Fatty acids from CH2O and amino acids -Cholesterol -Phospholipids -Lipoproteins -Ketones -Degradation of: -Fatty acids, phospholipids -Saturation, desaturation, lengthening, shortening, deposit of liver lipids -Biosynthesis of fatty acids -Active in adipose, liver and mammary tissues -Begins in Acetyl-CoA -Assembled in 2 carbon units -Animal tissue synthesizes up to 16 carbons -Desaturation in tissue is limited -Ruminant: -Glucose propionate lactate acetate Acetyl-CoA -Biosynthesis of Triglycerides -Acetyl-CoA + alpha-glycerol phosphate phospholipid + Acyl-CoA diglyceride + Acyl-CoA triglyceride -Triglyceride Catabolism -Adipose tissue -Composed primarily of adipose tissue -Dynamic tissue= synthesis and degradation of triglycerides -Lipoprotein lipase= hydrolysis of TG -Synthesized in many tissues -Activity high in fed state, low in fasted state -Activity under hormonal control -Lypolysis is stimulated by: beta-adrenergic agonists (paylean), adrenocortcotropins, somatotropin (GH) -Inhibited by: prostaglandins and insulin -Lypolysis is “break down of lipids” -Control of net fat accretion involves complex regulatory systems that include lypolysis and lipogenesis -Fatty Acid Catabolism -Fatty acids released from hydrolysis=transported to tissues as an oxidative energy source -Oxidation (beta oxidation and TCA cycle) occurs in the mitochondria (skeletal muscle, liver, cardiac muscle, adipose tissue, etc.) -Beta oxidation stepwise enzymatic removal of 2 carbon units (AcetylCoA) to be used for resynthesis of fatty acids, synthesis of steroids or ketones, entry into TCA cycle -Not reverse of synthesis process -Total energy with oxidation of a LCFA comes from both beta oxidation and Acetyl-CoA oxidation in TCA cycle -Steroid Metabolism -Cholesterol = most abundant sterol and precursor to most others -Biosynthesis of Acetyl-CoA -Partially controlled by dietary intake -Cholesterol excreted in bile -Used for sterol synthesis; progesterone, ACTH, testerone, estrogen -Phospholipid Metabolism -Lecithin (phosphatidyl choline) is most abundant in animal tissue -Ketone Metabolism -Formation of ketones is continous -Used as energy source in skeletal muscle and other peripheral tissue -Overproduction occurs in: -Disorders: diabetes mellitus -Low CH2O intake -Abnormalities in Lipid Metabolism -Fatty Livers -Dairy cattle in negative energy balance -Associated with excessive fat mobilization from adipose tissue -Fat deposited in liver (5%) slower net loss -Transition period important -Feeding protected choline -Ketosis -Overly fat animals, often seen in dairy cattle -Rapid mobilization of fat depot -Reduced intakes -Lack of ability to metabolize Acetyl-CoA in TCA cycle fast enough -Acetyl-CoA Acetoacetic acid acetone and B-hydroxybutric acid -Obesity -Over consumption of calories is a factor -Genetics plays a major role -Lipogenic enzyme activity in adipose tissue of obese animals higher -Net deposition is greater than normal -Cell size and number -Vary with species and individuals -Proliferation can occur postnatally