Biochemistry Of Lipid Metabolism

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Two Categories of Lipids

Back 1

1. Polar
2. Non-polar (Neutral)

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Major Categories of Lipids

Back 2

Triacyl Glycerols
Fatty Acids
Phospholipids
Glycolipids
Sphingolipids
Steroids
Vitamins (ADEK)

Front 3

Simple Triacyl Glycerol

Back 3

TG with unsaturated fatty acid

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Mixed Triacyl Glycerol

Back 4

2 or more different fatty acids

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Natural Oils

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TG with unsaturated fatty acids

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Solid Fat

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TG with saturated fat

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Bio Waxes

Back 7

-Esters of long chain FA with long chain alcohols
-high melting point

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Neutral Lipids

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TG
Natural Fats
Natural Oils
Solid Fats
Biological Waxes

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Saturated Lipids

Back 9

No Double Bonds
Non-H2O Soluble
Non-Aqueous
Solid @ room temp

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Unsaturated Lipids

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Double Bonds
Liquid @ room temp

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Fish Oils (omega-3)

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Increase Lipoprotein Lipase
Increase FA Oxidation
Inhibits TG Synthesis
Essential FA's

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Trans Fats

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Not kinked
Solid @ room temp
increase risk for heart disease/type 2 diabetes

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Polar Lipid

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Contains a Polar group:
Phosphate, Sulfate, Sugar
Amphipathic

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A Fat Cell

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Can Expand
Great longevity
9 g/Cal
Efficient Storage@ Anhydrous State

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Uses of Lipids

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Structure -> Phospholipids (membranes)

Communication -> Steroids

Enzyme Cofactors -> Vit. K

Digestion -> Bile Salts

Anti Oxidants -> Vit. E

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Strategies for Digestion

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1.Emulsification
(Bile Salts/mixing)

2.Solubilization
(detergents)

Front 17

Primary product of Lipid Digestion

(Digestion of Cholesterol,Phospholipid, TG)

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1. FFA
2. 2-monoacylglycerol
3. Cholesterol

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Micelle

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Form when polar lipids are added to H2O

Polar groups outward facing

Non-polar groups inward facing

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Emulsions

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Large Lipid Droplets
Visible Cloudiness
No Organized structure
Unstable
Can be stabilized by Emulsifying agents

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2 Types of Bile Salts

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1.Glycine

2.Taurine

Front 21

Bile Salts (structure)

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Sterol Ring + Taurine/Glycine

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Main Function of Bile Salts

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Make Micelles

Critical Micelle Conentration (CMC) 2-5mM

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Bile Salts

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Stored in Gall Bladder
Detergent
Needed for Cholesterol & Vitamin (AEK) Absorption

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Degrades Triacyl Glycerol

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Pancreatic Lipase

Front 25

Degrades Cholesteryl Esters

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Cholesteryl Ester Hydrolase

(produces Cholesterol + FFA)

Front 26

Degrades Phospholipids

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Phospholipase A2 (Pancreatic Juice)

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Pancreatic Lipase

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Removes 1&3 carbons making 2-monoacylglycerol

Needs Colipase (produced in pancreas)

Prefers long chain FA (greater than 12 C's)

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Phospholipase A2

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proenzyme is activated by trypsin

Phospholipase A2 hydrolizes FA @ carbon 2 of phospholipids

makes lysophospholipid (detergents)

remaining FA @ C1 is removed by lysophospholipase.

Lysophospholipase->glycophosphoryl base->feces/excretion

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5 main classes of lipoproteins

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1.chylomicrons
2.VLDL
3.IDL
4.LDL
5.HDL

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Apolipoprotiens

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Attach to lipoproteins for transport

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Orlistat

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Anti-Obesity drug
inhibits pancreatic and gastric lipases

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Olestra

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artificial fat, not degraded by pancreatic or gastric lipases.

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Activates LCAT

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Apo-A1

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Activates Lipoprotein Lipase

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Apo-CII

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Ligand for HDL Receptor

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Apo-A1

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Ligand for LDL Receptor

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Apo-B100

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Ligand for LDL receptor and remnant factor

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Apo-E

Front 38

stabilized by hydrophobic frces not covalent bonds

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apolipoprotein complexes

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Lipoprotein Lipase

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Located @ Capillary Walls of Tissues
Activated by Apo C-II
Hydrolyzes TG to make monoacylglycerol,glycerol, FA's

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Deficiency in Lipoprotein Lipase + C-II

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Accumulation of TG-rich lipoproteins in plasma

type-1 hyperlipidemia

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Chylomicron Remnants

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Loss of TG
decrease in size
increase in density
apo c-ii returned to HDL
taken up by endocytes
degraded to aa's, free cholesterol, glycerol, fa

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Enzyme for exchange between VLDL & HDL

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Cholesteryl Ester Transfer Protein (CETP)

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Abetalipoproteinemia

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ApoB not made
no Chylomicrons/VLDL in serum
Lipid droplets accumulate in liver/intestinal cells
Hypolipidemia

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HDL

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1. Reservoir for apolipoproteins
2. Synthesized in liver & released in blood stream (exocytosis)

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Enzyme for esterifying Cholesterol in HDL

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Phosphotidylcholine Cholesterol Acyl Transferase (LCAT/PCAT)

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Enzyme activated by Epinephrine, NE, Glucagon for metabolism of TG in tissues

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Hormone Sensitive Lipase

AKA Triacyl Glycerol Lipase

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Carries FFA in blood stream

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Serum Albumin

Front 48

Lacks Glycerol Kinase to metabolize free glycerol

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Adipocytes

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Catalyzes FA 'activation'

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Acyl CoA Synthetase

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Main Regulator of FA Oxidation & Inhibits CPT-1

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Malonyl CoA

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enzyme on the outer membrane of mitochondria

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Carnitine Palmitoyl transferase 1 (CPT-1)

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enzyme on the inner membrane of mitochondria

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Carnitine Palmitoyl transferase 2 (CPT-2)

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4 Steps of Beta Oxidation

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1. Oxidation
2. Hydration
3. Oxidation
4. Thiolisis (cleavage)

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Where does Acetyl CoA go after it is made in beta oxidation

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Citric Acid Cycle (10 ATP)

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Energy made per cycle of beta oxidation

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1 NADH
1 FADH2
1 Acetyl CoA

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Enzyme for oxidation of monounsaturated fat

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Enoyl CoA Isomerase

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2 enzymes for polyunsaturated fat oxidation

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1.Acyl CoA Dehydrogenase
2.2-4 DiEnoyl CoA Reductase

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Zellwegger Syndrome

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Accumulation of VLCFA
Peroxisomes not properly formed
Death 1st year

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Adrenoleukodystrophy

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Innability to transport VLCFA into peroxisomesVLCFA accumulates in brain
demylination of brain/degeneration of adrenal cortex
Psychomotor retardation/seizures

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Occurs in the peroxisomes of mainly Brain and other nervous tissues

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Alpha Oxidation

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C10-C14 Fatty Acids released in tissue in ketosis, no energy made

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Omega oxidation

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3 Compounds formed during Ketone body synthesis

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1. 3-hydroxybutyrate
2. Acetoacetate
3. Acetone

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rate limiting step for ketone body synthesis

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HMG CoA Synthase

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Enzyme for conversion of OAA to PEP

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PEP carboxykinase
(present in liver, absent in muscle and heart)

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How does Acetyl CoA get out of mitochondria

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Citrate acts as a carrier

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Main pathway for de novo synthesis of FA

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Cytosol

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Commited step in FA Synthesis

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Malonyl CoA formation

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enzyme for carboxylation of Acetyl CoA to make Malonyl CoA

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Acetyl CoA Carboxylase

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Acetyl Coa Contains...

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Biotin

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Hormone that activates FA Synthesis

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Insulin

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Hormone that inhibits FA Synthesis

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Glucagon

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2 Steps for Acetyl CoA Carboxylation

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1. Formation of carboxybiotin (needs ATP)

2. Activated CO2 group is transferred to acetyl CoA to make malonyl CoA

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Main purpose of Acyl Carrier Protein (ACP)

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Used for activation

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4 steps in FA Synthesis

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1. Condensation
2. Reduction
3. Dehydration
4. Reduction

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End product of FA Synthesis

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palmitate