molecule has the identical structure elements as carb but differs in its linkage and number of atoms. • The formula C57H110O16 describes the common lipid stearin with H:O ratio of 18.3:1 for carb , the ratio remains constant at 2:1. Lipid the general term for a heterogeneous group of compounds, includes oils, fats, waxes, and related compound. Oils become liquid at room temperature, whereas fats remain solid. PHYSIOLOGY – lipids 3 main groups 1. Simple - “neutral fats”, consists primarily of triacylglycerols. The fats are “neutral” because at the pH of the cell they carry no electrically charged groups. These completely nonpolar molecules have no affinity for water. 2. Compound – triacylglycerol components combined with other chemicals, represent about 10% of the body’s total fat content. 3. Derived lipids – simple and compound lipids form derived lipids. Cholesterol, the most widely derived lipid, exists only in animal tissue and from a dietary viewpoint classifies as a lipid. PHYSIOLOGY – lipids SIMPLE • A triglyceride (TG, triacylglycerol, TAG, or triacylglyceride) is an ester derived from glycerol and three fatty acids (from tri- and glyceride).[1] Triglycerides are the main constituents of body fat in humans and other animals, as well as vegetable fat.[2] They are also present in the blood to enable the bidirectional transference of adipose fat and blood glucose from the liver, and are a major component of human skin oils.[3] • There are many different types of triglyceride, with the main division between saturated and unsaturated types. Saturated fats are "saturated" with hydrogen — all available places where hydrogen atoms could be bonded to carbon atoms are occupied. These have a higher melting point and are more likely to be solid at room temperature. Unsaturated fats have double bonds between some of the carbon atoms, reducing the number of places where hydrogen atoms can bond to carbon atoms. These have a lower melting point and are more likely to be liquid at room temperature. PHYSIOLOGY – lipids SIMPLE • Triacylglycerols constitutes the major storage form of fat in fat cells (adipocytes) • fatty acid - is a carboxylic acid with a long aliphatic chain, which is either saturated or unsaturated. Most naturally occurring fatty acids have an unbranched chain of an even number of carbon atoms, from 4 to 28. Saturated fatty acid contains only single covalent bonds between carbon atoms; all of the remaining bonds attach to hydrogen. Saturated fatty acids occur primarily in animal products such as beef (52%), lamb, pork, chicken, egg yolk, & dairy fats of cream, milk,butter (62%) & cheese. Saturated fats from the plants include coconut oil & palm oil, vegetable shortening, and hydrogenated margarine; commercially made cakes, pies,& cookies contain plentiful amounts. PHYSIOLOGY – lipids SIMPLE A saturated fat is a type of fat in which the fatty acid chains have all or predominantly single bonds. A fat is made of two kinds of smaller molecules: glycerol and fatty acids. Fats are made of long chains of carbon (C) atoms. Some carbon atoms are linked by single bonds (-C-C-) and others are linked by double bonds (-C=C- ).[1] Double bonds can react with hydrogen to form single bonds. They are called saturated, because the second bond is broken and each half of the bond is attached to (saturated with) a hydrogen atom. Most animal fats are saturated. The fats of plants and fish are generally unsaturated.[1] Saturated fats tend to have higher melting points than their corresponding unsaturated fats, leading to the popular understanding that saturated fats tend to be solids at room temperatures, while unsaturated fats tend to be liquid at room temperature with varying degrees of viscosity (meaning both saturated and unsaturated fats are found to be liquid at body temperature). PHYSIOLOGY – lipids SIMPLE Unsaturated fatty acids contain one or more double bonds along their main carbon chain. An unsaturated fat is a fat or fatty acid in which there is at least one double bond within the fatty acid chain. A fatty acid chain is monounsaturated if it contains one double bond, and polyunsaturated if it contains more than one double bond. Where double bonds are formed, hydrogen atoms are subtracted from the carbon chain. Thus, a saturated fat has no double bonds, has the maximum number of hydrogens bonded to the carbons, and therefore is "saturated" with hydrogen atoms. In cellular metabolism, unsaturated fat molecules contain somewhat less energy (i.e., fewer calories) than an equivalent amount of saturated fat. The greater the degree of unsaturation in a fatty acid (i.e., the more double bonds in the fatty acid) the more vulnerable it is to lipid peroxidation (rancidity). Antioxidants can protect unsaturated fat from lipid peroxidation. PHYSIOLOGY – lipids SIMPLE peroxidation (rancidity); is the oxidative degradation of lipids. It is the process in which free radicals "steal" electrons from the lipids in cell membranes, resulting in cell damage. This process proceeds by a free radical chain reaction mechanism. Antioxidants can protect unsaturated fat from lipid peroxidation; are compounds that inhibit oxidation. Oxidation is a chemical reaction that can produce free radicals, thereby leading to chain reactions that may damage the cells of organisms. Antioxidants such as thiols or ascorbic acid (vitamin C) terminate these chain reactions. To balance the oxidative state, plants and animals maintain complex systems of overlapping antioxidants, such as glutathione and enzymes (e.g., catalase and superoxide dismutase), produced internally, or the dietary antioxidants vitamin C, and vitamin E. PHYSIOLOGY – lipids SIMPLE • Monounsaturated fatty acid; canola oil, olive oil (77%), peanut oil, and the oil in almonds, pecans & avocados • Polyunsaturated fatty acid; safflower, sunflower, soybean & corn oil. Linoleic acid (LA), a carboxylic acid, is a polyunsaturated omega-6 fatty acid, an 18-carbon chain with two double bonds in cis configuration. A shorthand notation like "18:2 (n-6)" or "18:2 cis-9,12" may be used in literature.[4] It typically occurs in nature as a triglyceride ester; free fatty acids, the form not combined with glycerol to form triglyceride, are typically low in foods.[5] It is very soluble in acetone, benzene, diethyl ether and ethanol.[2] Linoleic acid belongs to one of the two essential fatty acids, which means that the human body cannot synthesize it from other food components. PHYSIOLOGY – lipids SIMPLE • Hydrogenation – a chemical process that changes oils to semisolid fats by bubbling liquid hydrogen under pressure into vegetable oil. Firmer fats form because adding hydrogen increases the lipid’s temperature. Hydrogenated oil behaves like a saturated fat; most common are lard substittutes and margarine. PHYSIOLOGY – lipids SIMPLE Triacylglycerol formation • Esterification – triacylglycerol synthesis or process • Triacylglycerol synthesis increases following a meal for two reasons: 1. Food absorption increases blood levels of fatty acids and glucose 2. Relatively high levels of circulating insulin facilitate triacylglycerol synthesis. PHYSIOLOGY – lipids SIMPLE Triacylglycerol breakdown • The term hydrolysis (lipolysis) describes triacylglycerol catabolism to yield glycerol and the energy- rich fatty acid molecules The mobilization of fatty acids via lipolysis predominates under 4 conditions: 1. Low-to-moderate-intensity exercise 2. Low-calorie dieting or fasting 3. Cold stress 4. Prolonged exercise that depletes glycogen reserves PHYSIOLOGY – lipids SIMPLE • Lipolysis /lɪˈpɒlɪsɪs/ is the breakdown of lipids and involves hydrolysis of triglycerides into glycerol and free fatty acids. Predominantly occurring in adipose tissue, lipolysis is used to mobilize stored energy during fasting or exercise. • Free fatty acids: By-products of the metabolism of fat in adipose tissues PHYSIOLOGY – lipids SIMPLE • Lipolysis also occurs in tissues other than adipocytes; Hydrolysis of dietary triacylglycerol occurs in the small intestine, catalyzed by pancreatic lipase; lipoprotein lipase, an enzyme located on the walls of the capillaries, catalyzes the hydrolysis of the triacylglycerols carried by the blood’s lipoprotein. Adjacent adipose tissue and muscle cells “take up” the fatty acids released by the action lipoprotein lipase; these fatty acids are resynthesized to triacylglycerol for energy storage. PHYSIOLOGY – lipids SIMPLE Trans-fatty acids: the unwanted fat • Trans-fatty acids derive from the partial hydrogenation of unsaturated corn, soybean, or sunflower oil • Forms when one of the hydrogen atoms along the restructured carbon chain moves from its naturally occurring position to the opposite side of the double bond that separates 2 carbon atoms • Rich sources – vegetable shortenings, some margarines, crackers, candies, cookies, snack foods, fried foods, baked goods, salad dressings, and other processed foods made from partially hydrogenated vegetable oils. PHYSIOLOGY – lipids SIMPLE Trans-fatty acids: the unwanted fat • Health effects about trans-fatty acids centers on their possible detrimental effects on serum lipoprotein • A diet high in margarine and commercial baked goods and deep-fried foods prepared with hydrogenated vegetable oils increases low-density lipoprotein cholesterol concentration by a similar amount as a diet high in saturated fatty acids. • Hydrogenated oils also decrease the concentration of beneficial high-density lipoprotein cholesterol. PHYSIOLOGY – lipids SIMPLE Trans-fatty acids: the unwanted fat • The relationship between saturated fatty acid intake and coronary heart disease risk has prompted health professionals to recommend 2 courses of action: 1. Replacing at least a portion of the saturated fatty acids and all trans-fatty acids with nonhydrogenated monounsaturated and polyunsaturated oils 2. Balancing energy intake with regular physical activity to minimize weight gain and obtain the health benefits of regular exercise. PHYSIOLOGY – lipids COMPOUND LIPIDS • Triacylglycerol components combined with other chemicals, represent about 10% of the body’s total fat content. 3 groups 1. Phospholipids 2. Glycolipids 3. Lipoprotein PHYSIOLOGY – lipids COMPOUND LIPIDS • Phospholipids -are a class of lipids that are a major component of all cell membranes. They can form lipid bilayers because of their amphiphilic characteristic. The structure of the phospholipid molecule generally consists of two hydrophobic fatty acid "tails" and a hydrophilic "head" consisting of a phosphate group. The two components are joined together by a glycerol molecule. PHYSIOLOGY – lipids COMPOUND LIPIDS Phospholipids • Modified triacylglycerols, contains one or more fatty acid molecules joined with a phosphorus-containing group and one of several nitrogen-containing molecules. • These lipids form in all cells, although the liver synthesizes most of them. 4 main functions: 1. Interacting with both water and lipid to modulate fluid movement across cell membranes 2. Maintaining the structural integrity of the cell 3. Playing an important role in blood clotting 4. Providing structural integrity to the insulating sheath that surrounds nerve fibers. PHYSIOLOGY – lipids COMPOUND LIPIDS Phospholipids • Modified triacylglycerols, contains one or more fatty acid molecules joined with a phosphorus-containing group and one of several nitrogen-containing molecules. • These lipids form in all cells, although the liver synthesizes most of them. 4 main functions: 1. Interacting with both water and lipid to modulate fluid movement across cell membranes 2. Maintaining the structural integrity of the cell 3. Playing an important role in blood clotting 4. Providing structural integrity to the insulating sheath that surrounds nerve fibers. PHYSIOLOGY – lipids COMPOUND LIPIDS Glycolipids • are lipids with a carbohydrate attached by a glycosidic (covalent) bond. Their role is to maintain the stability of the cell membrane and to facilitate cellular recognition, which is crucial to the immune response and in the connections that allow cells to connect to one another to form tissues. • Fatty acids that bound with carbohydrate and nitrogen. PHYSIOLOGY – lipids COMPOUND LIPIDS Lipoprotein • any of a group of soluble proteins that combine with and transport fat or other lipids in the blood plasma. • Protein spheres formed primarily in the liver when a protein molecule joins with either triacylglycerols or phospolipids • provide the major avenue for transporting lipids in the blood; if blood lipids did not bind to protein, they would literally float to the top like cream in non-homogenized fresh milk instead of circulating throughout the vascular system. PHYSIOLOGY – lipids COMPOUND LIPIDS - Lipoprotein 4 types of Lipoprotein 1. Chylomicrons – form when emulsified lipid droplets leave the intestine and enter the lymphatic vessels; liver metabolizes chylomicrons and sends them for storage in adipose tissue; transport the fat-soluble vit A,D,E & K. 2. High-density lipoprotein (HDL) – produced in the liver and small intestine, they contain the highest % of protein (about 50%) and the least total lipid (about 20%) and cholesterol (about 20%) of the lipoprotein. PHYSIOLOGY – lipids COMPOUND LIPIDS - Lipoprotein 4 types of Lipoprotein 3. Very low-density lipoprotein (VLDL) – these are degraded in the liver to produce a LDL; formed in the liver from fats, carbohydrates, alcohol & cholesterol; contains the highest % of lipid(95%), of which about 60% consists of triacylglycerol; transport triacylglycerol to muscle and adipose tissue 4. Low-density lipoprotein(LDL) – commonly known as “bad” cholesterol; normally carries from 60-80% of the total serum cholesterol & has the greatest affinity for cells of the arterial wall. PHYSIOLOGY – lipids COMPOUND LIPIDS - Lipoprotein • Low-density lipoprotein(LDL) delivers cholesterol to arterial tissue where the LDL particles are: 1. Oxidize to alter their physiochemical properties 2. Taken up by macrophages inside the arterial wall to initiate atherosclerotic plaque development LDL oxidation ultimately contributes to smooth muscle cell proliferation and other unfavorable cellular changes that damage and narrow arteries. PHYSIOLOGY – lipids COMPOUND LIPIDS HDL vs LDL: a health perspective • Unlike LDL, HDL protects against heart disease • HDL acts as a scavenger in the reverse transport of cholesterol by removing it from the arterial wall and delivering it to the liver for incorporation into bile and subsequent excretion via the intestinal tract • Regular moderate & high-intensity aerobic exercise and abstinence from cigarette smoking increase HDL, lower LDL. PHYSIOLOGY – lipids DERIVED LIPIDS • Simple and compound lipids form derived lipids. • are the substances produced from simple and compound lipidsthrough the process of hydrolysis. There are many different types of derived lipids, including alcohols, monoglycerides, diglycerides, fatty acids, terpenes, steroids and carotenoids, with the last three groups being the most common. • Cholesterol, the most widely known derived lipid, exists only in animal tissue and from a dietary point of view classifies as a lipid. PHYSIOLOGY – lipids DERIVED LIPIDS - Cholesterol • Cholesterol does not contain fatty acids; instead it shares some of lipid’s physical and chemical characteristics • Widespread in the plasma membrane of all cells, originates either through; diet (exogenous cholesterol) and cellular synthesis (endogenous cholesterol) • endogenous cholesterol daily synthesis varies between 0.5 and 2.0 g even in a “cholesterol free” diet • More endogenous cholesterol forms with a diet high in saturated fatty acids and trans-fatty acids, which facilitates LDL cholesterol synthesis in the liver; the liver synthesizes about 70% of the body’s cholesterol PHYSIOLOGY – lipids DERIVED LIPIDS - Cholesterol Functions of cholesterol in bodily functions; 1. Building plasma membranes 2. Serving as a precursor in synthesizing vit D, adrenal gland hormones, and the sex hormones estrogen, androgen and progesterone 3. Furnishes a key component for bile synthesis 4. Plays a crucial role in forming tissues, organs, and body structures during fetal development Rich source of cholesterol; egg yolk, red meat, organ meats, shellfish, dairy products Foods of plant origin contain no cholesterol PHYSIOLOGY – lipids Recommended Lipid intake • Between 20 and 35% of caloric intake depending on the type of lipid consumed • Focus on weight control and addition of two weekly serving of fish high in omega-3 fatty acids • Diet that contains only 20% of total calories from lipid to reduce risk of cancers of the colon and rectum, prostate, endometrium, and perhaps breast. • Curtailing intake of animal food sources rich in saturated fatty acids reduces preformed cholesterol intake known to stimulate endogenous cholestrol synthesis. PHYSIOLOGY – lipids Role of lipid in the body 1. Energy source and reserve 2. Protection of vital organs 3. Thermal insulation 4. Vitamin carrier and hunger depressor PHYSIOLOGY – lipids Role of lipid in the body - Energy source and reserve • Fat constitutes the ideal cellular fuel for 3 reasons; 1. It carries a large quantity of energy per unit weight 2. It transports and stores easily 3. It provides a ready source of energy Fat provides as much as 80-90% of the energy requirement of a well-nourished individual at rest. 1 gram of pure lipid contains about 9cal of energy, twice that of carbs and protein Fat exists as a relatively water-free, concentrated fuel, whereas glycogen remains hydrated and heavy relative to its energy content For young adults, approximately 15% of the body mass of males and 25% of that of females consistsof fat. PHYSIOLOGY – lipids Role of lipid in the body Protection of vital organs and Thermal insulation • Up to 4% of the body’s fat protects against trauma to vital organs • Fat stored just below the skin (subcutaneous fat) provides insulation, permitting individuals to tolerate extreme cold • Excess body fat hinders temperature regulation during heat stress, most notably during sustained exercise in air, when the body’s heat production can increase 20x above resting levels; the insulatory shield from subcutaneous fat retard heat flow from the body. PHYSIOLOGY – lipids Role of lipid in the body Vitamin carrier and hunger depressor • Consuming approximately 20 g of dietary fat provides a sufficient source and transport medium for the fat soluble vit A,D,E & K • Severely reducing lipid intake depresses the body’s level of vitamins and ultimately leads to vit deficiency • Dietary lipid also facilitates absorption of vit A precursors from nonlipid plant sources • It takes about 3.5 hrs after ingesting lipids for the stomach to empty them. PHYSIOLOGY – lipids Fat Dynamics during exercise Intracellular and extracellular fat supply between 30 and 80% of the energy for physical activity, depending on nutritional and fitness status and exercise intensity and duration. • Increased blood flow through adipose tissue with exercise increases the release of FFAs ( free fatty acids) for delivery to and use by muscle. • The quantity of fat used for energy in light and moderate exercise is 3x that compared to resting conditions. • As exercise becomes more intense ( greater 5 of aerobic capacity), adipose tissue release of FFAs fails to increase much above resting levels, leading to a decrease in plasma FFAs. • this in turn stimulates increased muscle glycogen used. PHYSIOLOGY – lipids Fat Dynamics during exercise • The energy contribution from intramuscular triacylglycerols ranges between 15 & 35%, with endurance-trained athletes catabolizing the largest quantity and a substantial impairment in use among the obese/type 2 diabetics • Long-term consumption of a high-fat diet induces enzymatic adaptations that enhance fat oxidation during submaximal exercise; this adaptation does not translate to improved exercise performance PHYSIOLOGY – lipids Fat Dynamics during exercise The major energy for light to moderate exercise comes from fatty acids released from triacylglycerol storage sites and delivered to muscle as FFAs and intramuscular triacylglycerol. • The start of exercise produces a transient initial drop in plasma FFA concentration because of increased FFA uptake by active muscles • An increased FFA release from adipose tissue follows owing to: 1. Hormonal stimulation by the sympathetic nervous system 2. A decrease in plasma insulin levels. PHYSIOLOGY – lipids Fat Dynamics during exercise During moderate intensity exerrcise, approximately equal amounts of carb and fat supply energy; when exercise continues at this level for more than 1 hr, fat catabolism gradually supplies a greater % of energy; this coincides with the progression of glycogen depletion Carbohydrate availability also influences fat use for energy • With adequate glycogen reserves, carbohydrate becomes the preferred fuel during intense aerobic exercise because of its more rapid rate of catabolism • Toward the end of prolonged exercise ( glycogen nearly depleted), fat, mainly as circulating FFA, supplies 80% of the total energy requirement. PHYSIOLOGY – lipids Fat Dynamics during exercise The increase in fat catabolism during prolonged exercise probably results from a small drop in blood sugar and decrease in insulin ( a potent inhibitor of lipolysis), with a corresponding increase in glucagon output by the pancreas • In the first hour, fat supplied about 50% of the energy; by the third hour, fat contributed up to 70% of the total energy requirement PHYSIOLOGY – lipids Fat Dynamics during exercise Exercise intensity govern fat’s contribution to the metabolic mixture Increased exercise intensity produced an eventual crossover in the balance of fuel use – total energy from all sources of fat breakdown remained essentially unchanged • More intense exercise required added energy from blood glucose and muscle glycogen • Total energy from fats during exercise at 85% of maximum did not differ from exercise at 25% Highlight the major role of carbohydrate, primarily muscle glycogen, plays as a preferential fuel for high- intensity aerobic exercise PHYSIOLOGY – lipids Exercise training and Fat use • Regular aerobic exercise profoundly improves long- chain fatty acid oxidation, particularly from triacylglycerols within active muscle, during mild-to- moderate-intensity exercise 7 factors that can produce trng-induced increases in fat catabolism in exercise; 1. Facilitated fatty acid mobilization from adipose tissue through increased rate of lipolysis within adipocytes 2. Proliferation of capillaries in trained muscle that increases the total number and density of these microvessels for energy substrate delivery 3. Improved transport of FFAs through the muscle fiber’s plasma membrane PHYSIOLOGY – lipids Exercise training and Fat use 4. Increased fatty acid transport within the muscle cell, mediated by carnitine and carnitine acyltransferase 5. Increased size and number of mitochondria 6. Increased quantity of enzymes involved in ß- oxidation, citric acid cycle metabolism, and the electron-transport chain within specifically trained muscle fibers 7. Maintenance of cellular integrity and function, which enhances endurance performance independent of conservation of glycogen reserves. PHYSIOLOGY – lipids Summary • Saturated fatty acids contain as many hydrogen atoms as chemically possible; saturated describes this molecule with respect to hydrogen. Saturated fatty acids exist primarily in animal meat, egg yolk, dairy fats, & cheese. A large saturated fatty acid intake elevates blood cholesterol concentration and promotes coronary heart disease. • Unsaturated fatty acids contain fewer hydrogen atoms attached to the carbon chain. Unlike saturated fatty acids, double bonds connect carbon atoms; these fatty acids are either monounsaturated or polyunsaturated with respect to hydrogen. Increasing the diet’s proportion of unsaturated fatty acids protects against coronary heart disease. • Lowering blood cholesterol ( esp. that carried by LDL cholesterol) provides significant heart disease protection. PHYSIOLOGY – lipids Summary • Dietary lipid currently provides about 36% of total energy intake. Prudent recommendation suggest a level of 30% or less for dietary lipid, of which 70 to 80% should consists of unsaturated fatty acids. • Lipids provide the largest nutrient store of potential Energy for biologic work. They also protect vital organs, provide insulation from the cold, and transport the four fat-soluble vits A,D,E, % K. • Fat contributes 50-70% of the energy requirement during light & moderate-intensity exercise. Stored fat ( intramuscular and derived from adipocytes) plays an increasingly important role during prolonged exercise. Fatty acid molecules (mainly circulating FFAs) provide more than 80% of the exercise energy requirements. PHYSIOLOGY – lipids Summary • Carbohydrate depletion reduces exercise intensity to a level determined by how well the body mobilizes and oxidizes fatty acids. • Aerobic trng increases long-chain fatty cid oxidation during mild to moderate intensity exercise, primarily fatty acids from triacylglycerols within active muscle. • Enhanced fat oxidation with trng spares glycogen; this allows trained individuals to exercise at a higher absolute level of submaximal exercise before they experience the fatiguing effects of glycogen depletion.