Triacylglycerols excess

Animal fats and vegetable oils are triacylglycerols, or triesters, formed from the reaction of glycerol (1,2, 3-propanetriol) with three long-chain fatty acids. One of the methods used to characterize a fat or an oil is a determination of its saponification number. When treated with boiling aqueous KOH, an ester is saponified into the parent alcohol and fatty acids (as carboxylate ions). The saponification number is the number of milligrams of KOH required to saponify 1.000 g of the fat or oil. In a typical analysis, a 2.085-g sample of butter is added to 25.00 ml of 0.5131 M KOH. After saponification is complete, the excess KOH is back titrated with 10.26 ml of0.5000 M HCl. What is the saponification number for this sample of butter ... 

Saponification (see Section 7.4) is carried out to extract more recalcitrant lipids, and the yields are higher than for conventional solvent extraction (Stern et al. 2000). 3 ml of 0.5 M methanolic NaOH is added to 0.1 g of the shard powder and heated at 70°C for 3 hours in a sealed glass vial. After cooling, the supernatant is acidified with HC1 and extracted with three aliquots of 3 ml //-hexane. The hexane will not mix with the methanolic solution (unlike the DCM MeOH used above), but will absorb the lipids and can be transferred into a new clean vial. The removal of excess hexane is carried out as above. Saponification will hydrolyze and methylate any ester functionalities, which removes the requirement to derivatize the samples (Section 7.4) unless other molecules are suspected of being present. However, any wax esters or triacylglycerols will also be hydrolyzed to their fatty acid methyl esters and alcohols therefore, if information on their composition is required, then conventional solvent extraction is recommended as a first step. For subsequent characterization of the lipid extract, see Chapter 7. 

Triacylglycerol in the forms of chylomicrons or very low density lipoproteins constitutes the mass transport system of fat in the blood. Excessive levels, particularly of VLDL, can give rise to various pathological problems which are grouped together under the title lipoproteinaemias and are discussed in Chapter 11 (Appendix 11.9). 

Synthesis of fatty acids and their incorporation into triacylglycerols are stimulated during this time of energy excess. 

Malonyl-CoA, the first intermediate in the cytosolic biosynthesis of long-chain fatty acids from acetyl-CoA (see Fig. 21-1), increases in concentration whenever the animal is well supplied with carbohydrate excess glucose that cannot be oxidized or stored as glycogen is converted in the cytosol into fatty acids for storage as triacylglycerol. The inhibition of carnitine acyltrans-ferase I by malonyl-CoA ensures that the oxidation of... 

When a cell or organism has more than enough metabolic fuel to meet its energy needs, the excess is generally converted to fatty acids and stored as lipids such as triacylglycerols. The reaction catalyzed by acetyl-CoA... 

The function of the apparently futile triacylglycerol cycle (futile cycles are discussed in Chapter 15) is not well understood. However, as we learn more about how the triacylglycerol cycle is sustained via metabolism in two separate organs and is coordinately regulated, some possibilities emerge. For example, the excess capacity in the triacylglycerol cycle (the fatty acid that is even-... 

When the diet contains more fatty acids than are needed immediately as fuel, they are converted to triacylglycerols in the liver and packaged with specific apolipoproteins into very-low-density lipoprotein (VLDL). Excess carbohydrate in the diet can also be converted to triacylglycerols in the liver and exported as VLDLs (Fig. 21-40a). In addition to triacylglycerols, VLDLs contain some cholesterol and cholesteryl esters, as well as apoB-100, apoC-I, apoC-II, apoC-III, and apo-E (Table 21-3). These lipoproteins are transported in the blood from the liver to muscle and adipose tissue, where activation of lipoprotein lipase by apoC-II causes the release of free fatty acids from the VLDL triacylglycerols. Adipocytes take up these fatty acids, reconvert them to triacylglycerols, and store the products in intracellular lipid droplets myocytes, in contrast, primarily oxidize the fatty acids to supply energy. Most VLDL remnants are removed from the circulation by hepatocytes. The uptake, like that for chylomicrons, is... 

They transport the newly formed triacylglycerols from the liver to other body cells including the adipocytes, which store excess fat (Fig. 21-1). 

Under conditions of nutritional excess, fatty acids are absorbed by adipose tissue where they are converted to storage lipids in the form of triacylglycerols. The triacylglycerols can be mobilized at a later time, when the carbohydrate... 

Synthesis and degradation of triacylglycerols in adipose tissue. Fatty acids are delivered to adipose tissue. In times of energy excess these are converted to triacylglycerols and stored until needed, at which point the triacylglycerols are converted back to fatty acids. 

Individuals who are overweight or obese primarily have excess adiposity or excess storage of triacylglycerols. The most common cause for patients being overweight is that the individual consumes more calories than are consumed for basic metabolic needs and energy expenditure. For each additional 3500 kcal consumed that are not utilized as fuel, 1 pound of fat is accumulated in the body. 

Figure 23-2. Metabolism in the fed state. An adequate supply of carbohydrate provides glucose to replenish glycogen stores. Dietary protein provides amino acids for protein synthesis. Dietary carbohydrates, fats, and proteins can all be metabolized to generate ATP. (For clarity, ATP generation during P-oxidation of fatty acids and substrate-level phosphorylation during glycolysis is not depicted.) Excess dietary carbohydrates and amino acids are converted to fatty acids and, along with excess dietary fatty acids, stored as triacylglycerols. DHAP, dihydroxyacetone phosphate.

Excess acetate (C2) can be converted to the mobile ketone body energy source aceto-acetate (C4) and thence its reduced form hydroxybutyrate (C,) for transport throughout the body. Excess acetate can be carboxylated (via acetylCoA carboxylase) to form malonylCoA (C3), the donor for further C2 additions (with C02 elimination) in the anabolic synthesis of long chain fatty acids. Fatty acids are components of the phospholipids of cellular membranes and are also stored as triacylglycerols (triglycerides) for subsequent hydrolysis and catabolic fatty acid oxidation to yield reduced coenzymes and thence ATP (see Chapter 2). 

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