Oxidation of Fatty Acids and Ketone Bodies

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1

Fatty acids oxidized as fuels are principally...

long-chain fatty acids released from adipose tissue triacylglycerol stores

2

major fatty acids that are oxidized:

palmitate, oleate, and stearate

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lipolysis is activated by

decreased insulin levels
increased levels of insulin couterregulatory hormones
glucagon, epinephrine, norepinephrine

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Energy is derived from oxidation of fatty acids to

acetyl CoA in the pathway of B-oxidation

5

triacylglycerols

three fatty acids esterified to a glycerol backbone

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lipases

enzymes that release long-chain fatty acids from adipose tissue during fasting and other conditions of metabolic need

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Albumin

a major serum protein that transports the hydrophobic fatty acids

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fatty acids must be activated to ____ before they can participate in B-oxidation and other pathways

acyl CoA derivatives
the fatty acid reacts with an ATP to form a high-energy fatty acyl AMP and pyrophosphate
AMP is then exchanged for CoA
Pyrophosphate bond is later used for energy

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Carnitine

serves as the carrier that transports activated long-chain fatty acyl groups across the inner mitochondrial membrane
when the transport is done, it returns to the cytosolic side of the membrane
highest affinity is seen in skeletal muscle cells

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Carnitine acyl transferases

reversibly transfer an activated fatty acyl group from CoA to carnitine to form an acylcarnitine ester

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Four types of rxns in the B-oxidation pathway

oxidation
hydration
oxidation
carbon-carbon bond cleavage

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unsaturated fats have a higher/lower melting point than saturated fats

lower
saturated fats are usually solid at room temperature

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three fatty acids essential in diet

arachidonic, linoleic, linolenic

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fatty acyl CoA synthetase

catalyzes the rxn of a long chain fatty acid (ex. palimitic acid) being activated by a linkage to CoASH
there are different fatty acyl CoA synthetases for the different length chains

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B-oxidation occurs in the

mitochondrial matrix

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energy yield of B-oxidation of 1 mol palmitic acid (16:0)

formation of palmitoyl CoA -2 ATP
7 FAD(2H) @ 1.5 ATP each 10.5 ATP
7 NADH + H+ @ 2.5 each 17.5 ATP
8 acetyl CoA @ 10 each 80 ATP
Total: 106 ATP

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for unsaturated fatty acids to undergo B-oxidation,

their cis double bonds must be isomerized to trans double bonds
or the double bond must be reduced

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odd-number of carbon chains undergo B-oxidation until the last spiral when 5 carbons remain in the fatty acyl CoA and create

propionyl CoA, a 3 carbon structure, which through a series of steps can be converted into succinyl CoA

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the energy yield from unsaturated fatty acids is lower because

it has to be oxidized first which requires energy

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very long chain and branched chain fatty acids are...

broken down in the peroxisomes until they are more manageable

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Fatty Acyl CoA -> Trans Delta2 Fatty Enoyl CoA

Acyl CoA Dehydrogenase

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Trans Delta2 Fatty Enoyl CoA -> L-B-Hydroxy Acyl CoA

Enoyl CoA Hydratase

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L-B-Hydroxy Acyl CoA -> B-Keto Acyl CoA

B-Hydroxy Acyl CoA Dehydrogenase

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B-Keto Acyl CoA -> Fatty Acyl Co A & Acetyl CoA

B-Keto Thiolase

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Fatty Acyl CoA ->

Trans Delta2 Fatty Enoyl CoA

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Trans Delta2 Fatty Enoyl CoA ->

L-B-Hydroxy Acyl CoA

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L-B-Hydroxy Acyl CoA ->

B-Keto Acyl CoA

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B-Keto Acyl CoA ->

Fatty Acyl CoA & Acetyl CoA