lipid biochem overview Flashcards
· Identify the structures of fatty acids, phospholipids, cholesterol and cholesterol esters.
fatty acids: most polar, carbon chain with carboxyl group at one end. Phospholipids: intermediate polarity, fatty acid connected to phosphate group. Cholesterol: intermediate polarity, steroid structure. Cholesterol ester: most non-polar, steroid structure with COOR
· Describe the chemical properties of each of these lipids
Cholesterol esters are so non polar it exists away from water in a droplet within cells or in center of circulating lipoproteins in plasma. Phospholipids and free cholesterol tend to be located at the interface of lipid and aqueous in membranes or at the surface of lipoproteins. Free fatty acids move in aqueous environments complexed to protein.
· Describe the sources of each lipid class and the general functions of each.
fatty acids: product of pancreatic digestion and bile salt emulsification of dietary lipids. Phospholipids: come from dietary lipids unchanged. Cholesterol: comes from breakdown of cholesterol ester by cholesteryl esterase and bile salts. Cholesterol ester: comes from dietary lipids unchanged
describe de novo lipogenesis
excess glucose in liver or adipose > glycolysis >Acetyl CoA (mitochondria) > citrate > Acetyl CoA (cytoplasm) > malonyl CoA (acetyl CoA carboxylase,rate limiting) > units of Acetyl CoA put together to form fatty acid chain (fatty acid synthase)
Malonyl CoA as regulator
Inhibits oxidation of fatty acids (the reverse of de novo lipogenesis)
energy source for fatty acid synthase
NADPH
fates of fatty acids
Fatty acids can be packaged with glycerol into triglyceride which circulates in the blood as VLDL triglyceride. This triglyceride can be taken up by adipose tissue through the action of lipoprotein lipase where it can be stored to be used when the body is in negative energy balance.
describe beta oxidation
low insulin, high counter-regulatory hormones > triglyceride in adipose tissue broken down (hormone sensitive lipase) > fatty acids/glycerol taken up by liver > glycerol used as substrate for gluconeogenesis and fatty acid is converted to acyl-carnitine then transported into mitochondria by carnitine palmitoyl transferase 1 (CPT1- rate limiting) > Acetyl CoA from fatty acyl CoA enters TCA cycle
When does beta oxidation occur
When the body is in negative energy balance such as occurs during short-term fasting or during exercise. Fat is used as alternate fuel for muscle and liver to preserve glucose for the brain, and provides ATP to fuel gluconeogenesis
describe ketogenesis
fatty acids or ethanol is converted to ketones. Rate limiting step in ketogenesis is the synthesis of hydroxyl methylglutaryl CoA by HMG CoA synthase
When does ketogenesis occur
If insulin is very low or absent and counter-regulatory hormones quite high such as occurs during long-term fasting, keto diets or diabetic/alcholic ketoacidosis. Ketones serve as alternate fuel for brain and other tissues in states of prolonged glucose insufficiency.
3 conditions of ketogenesis
- very low insulin levels, 2. high counter-regulatory hormones, 3. An abundant source of substrate: fatty acids in the case of fasting and diabetic ketoacidosis, and ethanol in the case of alcoholic ketoacidosis.
ketones are only formed when…
acetyl CoA produced by fatty acid metabolism (or ethanol metabolism) exceeds the capacity of the TCA cycle to metabolize it (ATP/ADP is high)
describe cholesterol synthesis
Cholesterol is synthesized from acetyl CoA through the formation of hydroxymethyl glutaryl CoA. The rate limiting step in this pathway is HMG-CoA reductase. This reaction occurs in the cytosol and uses NADPH for energy.
List 4 classes of specialized lipids
phospholipids, sphingolipids, glycospingolipids, arachadonic acid derivatives (leukotrienes or prostaglandins/thromboxanes)