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Biochem Test 1:4
Fatty Acid Nomenclature, Synthesis, B-oxidation, & Ketogenesis
71
Biochemistry
Undergraduate 3
03/01/2011

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Cards

Term
What are the four fat soluble vitamins?
Definition
A D E K
Term
Draw a TAG
Definition
O
H-C-O-C-R-CH3
| O
H-C-O-C-R-CH3
| O
H-C-O-C-R-CH3
Term
Draw a condensed structure of palmitic acid
Definition
16:0

COOH-CH2(14)-CH3
Term
Draw a condensed structure of stearic acid
Definition
18:0

COOH-CH2(16)-CH3
Term
What is the notation for oleic acid?
Definition
18:1 w-9
Term
What is the notation for linoleic acid?
Definition
18:2 w-6

*essential

can be made into many other omega 6 fatty acids (ie, gamma linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid)
Term
What is the notation for gamma linolenic acid?
Definition
18:3 w-6
Term
Which carbon in a fatty acid is Carbon 1?

Which end is the omega end?
Definition
The carboxyl carbon is carbon 1

The methyl end is the omega end
Term
What is the notation for dihomo-gamma-linolenic acid?
Definition
20:3 w-6
Term
What is the notation for arachidonic acid?
Definition
20:4 w-6
Term
What is the notation for alpha linolenic acid?
Definition
18:3 w-3

*essential

can be made into other omega 3's
EPA- Eicosapentaenoic Acid

DHA- Docosahexaenoic Acid
Term
The prefix dihomo- indicates what?
Definition
That it is 2 carbons longer
Term
What is the notation for eicosapentaenoic acid?
Definition
20:5 w-3
Term
What is the notation for docosahexaenoic acid?
Definition
22:6 w-3
Term
What two saturated acids do we need to know?
Definition
Stearic

Palmitic
Term
What is the monounsaturated acid we need to know?
Definition
Oleic
Term
What are the omega-6 FAs we need to know?
Definition
linoleic acid, gamma linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid
Term
MAO (stands for)
Definition
Monoamine Oxidase
Term
What AA can carnitine be made from?
Definition
Lysine
Term
How many ATPs can 1 acetyl coA make?
Definition
10 ATPs
Term
How many ATPs is an FAD2H worth?
Definition
1.5 ATPs
Term
How many ATPs is each NADH worth?
Definition
2.5 ATPs
Term
How many ATPs does activating a fatty acid cost?
Definition
2 ATPs

Beta Oxidation Net Rxn:
-->
Term
Formula for calculating ATP yield from a FA, and net ATP yield.
Definition
Divide the number of C’s by 2 and multiply by 10
Subtract one from ½ number of C’s and multiply by 2.5 for NADH and 1.5 for FAD2H

Net Yield = ATP Yield - 2 ATPs
Term
Objective 9f: AMP-PK stands for, is activated by, and function
Definition
Adenosine Mono Phosphate-Protein Kinase
activated by
AMP

Phosphorylates acetyl CoA carboxylase, inactivating it
Term
HMG coA stands for
Definition
3-Hydroxy-3-methyl glutaryl CoA
Term
Draw acetoacetate
Definition
CH3
C=O
CH2
COO-
Term
ACP stands for
Definition
acyl carrier protein
Term
What AA provides the sulfur for CoA?
Definition
Cysteine
Term
Name the seven enzymes that are responsive to insulin
Definition
Glucokinase

Acetyl CoA carboxylase

Fatty acid synthase

Citrate lyase

Malic enzyme

Glucose 6-P dehydrogenase (first enzyme in pentose-P pathway)

Liver pyruvate kinase (PEP to pyruvate)
Term
Examples of lipids (7)
Definition
TAGs, glycolipids, FAs, Cholesterol + other steroids, fat soluble vitamins A D E K, CoQ
Term
Why is cholesterol a special lipid?
Definition
It's amphipathic
Term
Four locations TAGs are found
Definition
Adipoctyes, chylomicrons, VLDL, lipoproteins
Term
What three functions do TAGs have?
Definition
Energy, Provides insulation thermally and mechanically
Term
How to tags travel?
Definition
Bind to proteins; broken down by lipases

Albumin carries FAs
Term
Chylomicrons vs VLDL
Definition
VLDL from place to place

Chylomicrons from food through lymph to blood
Term
What role does PKA have in adipocytes?
Definition
Phosphorylate/activate Hormone sensitive lipase
Term
What does synthetase imply?
Definition
ATP will be involved
Term
Net FA + coA rxn?
Definition
FA + CoA + 2ATP → fattyacylCoA + 2 ADP + 2Pi

Really breaks down ATP to AMP and PPi but additional rxns make it net.
Term
Desaturase Elongase Spiral (6 molecules 5 rxns)
Definition
18:3 ω-3


↓ Δ6 desaturase


18:4 ω-3


↓ elongase


20:4 ω-3


↓ Δ5 desaturase


20:5 ω-3


↓ elongase


22:5 ω-3


↓ Δ4 desaturase


22:6 ω-3
Term
FA degradation (B-oxidation) vs Synthesis
Definition
Fatty Acid Degradation
(β-oxidation) Fatty Acid Synthesis

mitochondrial matrix||| cytosol


CoA||| CoA and ACP


some dehydrogenases||| acetyl CoA carboxylase
(and a couple more)||| synth:fatty acid synthase


no malonyl CoA ||| malonyl CoA


FAD and NAD+ are ||| NADPH is the
the oxidizing agents||| reducing agent
Term
B-ox rxns vs Synth rxns
Definition
β-oxidation||| fatty acid synthesis

saturated||| saturated

↓oxidation||| ↑reduction

α,β-unsaturated ||| α,β-unsaturated

↓add H2O ||| ↑lose H2O

β-hydroxy||| β-hydroxy

↓oxidation||| ↑reduction

β-keto||| β-keto
↓lose C1 & C2||| ↑add C1 & C2

saturated||| saturated
Term
Summarize ways that appearance of citrates in the cytosol promotes fatty acid synthesis
Definition
inhibits PFK-1 and causes the pentose-P pathway to increase due to equilibrium shifts that increase F 6-P, then G 6-P and so on

also speeds up acetyl CoA to malonyl coA
Term
Describe the mechanism by which malonyl CoA prevents the beta-oxidation of fatty acids in a cell
Definition
It inhibits Carnitine Palmitoyl Transferase I (aka, CPT I, or as Littleton says “CAT I”)
Term
Malonyl CoA level should be ___ in the fasting state, and ___ in the fed state
Definition
Malonyl CoA level should be low in the fasting state, and high in the fed state
Term
Describe the mechanism by which insulin signals inhibit beta-oxidation in liver cells
Definition
Insulin indirectly activates acetyl CoA carboxylase which turns acetyl coA to malonyl CoA which inhibits the CAT I enzyme which is a part of the overall B-ox rxn
Term
Draw acetone
how/why is it in the body?
Definition
m
C=O
m

made non-enzymatically and irreversibly from acetoacetate (equilibrial breakdown)
Term
Name the two ketone bodies that are useful

what does β-hydroxybutyrate dehydrogenase do?
Definition
B-hydroxybutyrate

Acetoacetate

β-hydroxybutyrate dehydrogenase interconverts acetoacetone and β-hydroxybutyrate
Term
How are Ketones used?
Definition
D-B-Hydroxybutyrate is converted to Acetoacetate (or it already is aa) which is then switched with succinate in succinyl coA via succinyl coA transferase --> making acetoacetyl coA which is then made into two acetyl coA molecules <-THIOLASE->
Term
Events that promote hepatic ketogenesis (10)
Definition
a decrease in the insulin level in the blood
and an increase in the glucagon level in the blood

an increase in the supply of fatty acids from adipose

an increase in beta oxidation of fatty acids in liver cells

an increase in NADH and acetyl CoA in mitochondria of liver cells




the high NADH (high NADH/NAD+ ratio)

oxaloacetate becomes unavailable for reaction with acetyl CoA




the high acetyl CoA and unavailability of oxaloacetate

increased use of the acetyl CoA to make ketone bodies

Also: mitochondrial HMG-CoA synthase is induced in fasting
Term
Can liver cells use ketone bodies?
Definition
Liver cells can’t use ketone bodies Because liver cells don’t have acetoacetate coA transferase, liver cells don’t have the gene for it and do not create it
Term
Main rate controller of TAG synthesis
Definition
Acetyl CoA Carboxylase
Term
Describe where fatty acids are mainly synthesized in humans, and the major source of carbons for building the fatty acids
Definition
The liver, glucose is the major source
Term
NADPH role
Definition
used by FA synthase as a reducing agent, and won’t use NADH
Term
Role of malic enzyme
Definition
reduces NADP+ to NADPH, releasing CO2, and turns malate to pyruvate
Term
What two sources of NADPH?
Definition
Malic Enzyme rxn

First rxn of pentose phosphate
Term
Malonyl CoA function?
Definition
Donates acetyl groups to FA's
Term
acetyl coA carboxylase rxn (3)
Definition
Acetyl CoA to Malonyl CoA
ATP to ADP + PPi
Co2 in
BIOTIN cofactor
Mg2+ cofactor
Term
Citrate lyase vs citrate synthase
Definition
Reverse of citrate synthase but costs an ATP
Term
Liver Glycerol 3-P production vs Adipocyte G3P production
Definition
Liver can phosphorylate glycerol --glycerol kinase--> G3P and:

Adipocytes can only use glucose to make DHAP and <--Trios Phosphate Isomerase--> G3P (uses NADH to NAD+)

liver cells do both
Term
Give the sequence of reactions that form a triacylglycerol from glycerol 3-phosphate and “activated” fatty acids
Definition
G3P -two FAcoA-> Posphatidic acid (2 FAs on glycerol with a phosphate) --> DAG --> TAG --> adipose stores or VLDL
Term
coA carboxylase regulation (4)
Definition
insulin (activates phosphotase) and citrate

glucagon (PKA phosphorylates/deactivates), palmitoyl CoA inhibits
Term
ACP has what vitamin in it?
Definition
Pantothenate
Term
Practice drawing figure 33.20 on p. 618 (liver picture)
Definition
-
Term
How do FAs get into mitochondrial matrix?
Definition
Carnitine Shuttle
Term
Acyl CoA Synthetase rxn
Definition
FA (most likely palmitate) + CoA --ATP to AMP + PPi--> FAcoA
Term
Carnitine palmitoyl transferase I (CAT I) rxn
Definition
replaces coA with carnitine in FAcoA inbetween outer and inner mitochondrial membranes

FAcoA --> Fatty acyl carnitine
Term
Carnitine palmitoyl transferase II (CAT II) rxn
Definition
Reverses CAT I rxn

FAcarnitine to FAcoA in mitochondrial matrix
Term
Acylcarnitine translocase function
Definition
Carnitine out of matrix into inter membrane space

FAcarnitine out of inter membrane space into matrix
Term
Process of Ketone Production (3 rxns 4 potential rxns two potential end products)
Definition
2 acetylCoA <--Thiolase--> Acetoacetyl CoA (coA gets thrown away) --HMG coA synthase--> 3-Hydroxy-3-Methylglutaryl CoA (HMG CoA) --HMG CoA Lyase--> Acetyl CoA (thrown away) and Acetoacetate

POSSIBLE REVERSIBLE: Acetoacetate <--D-B-hydroxybutyrate dehydrogenase NADH to NAD+--> D-B-hydroxybutyrate

Possible Irreversible: Acetoacetate --spontaneous--> Co2 + acetone (waste)
Term
enzymes of B-ox (4)
Definition
acyl coA dehydrogenase

enoyl CoA hydratase

B-hydroxy acyl coA dehydrogenase

B-keto thiolase
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