Biosynthesis Of Fatty Acids Flashcards

1
Q

Breakdown and synthesis of FAs are two separate pathways

What significant intermediate for synthesis is not present for breakdown and irreversible formation?

A

Malonyl coA

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2
Q

What are the active sites of acetyl coA carboxylase?

A

Biotin carboxylase domain

Activates co2
Attaches co2 to nitrogen in biotin ring with ATP help

Transcarboxylase domain
Transfers co2 from biotin to acetyl coA

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3
Q

Malonyl vs acetyl coA

A

Acetyl coA precursor
Just acetyl group plus s plus coA

Malonyl coA same as acetyl but plus co2
COOH group on end

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4
Q

Acetyl coA carboxylase differences in different species

Acetyl coA take hco3

A

Animal cells = cytoplasm for all steps

Bacteria = similar processs but separate polypeptide subunits for the three steps

Plants = both types

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5
Q

Why are fatty acids important?

A

Complex lipids components
E storage
Membrane structure
Signaling molecules

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6
Q

What is RLS for FA synthesis?

What is step stimulated by? Inhibited by?

A

Malonyl carboxylase synthesis

Stimulated by citrate
Inhibited by palmitoyl CoA

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7
Q

Biotinidase deficiency

A

Cannot recycle biotin

Enlarged liver and spleen
Dermatitis

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8
Q

Mammals FAS I details

A

Fatty acid synthase I
Multimeric complex = ensures efficiency
Only synthesizes even chain fatty acids

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9
Q

Sequence of events for FA synthase

A

KS = acetyl or Malonyl group added to ACP

condensation - co2 released (same co2 as added to acetylCoA in Acetyl coA carboxylase reaction)

KR = reduction of beta keto group (NADPH)

DH = dehydration - h2o released

ER = reduction of double bond (NADPH)

KS = translocation of butyryl group (resulting FA) to cys (SH) on KS

Recharge ACP with new Malonyl group

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10
Q

ACP Details

A

Contains covalent prosthetic group = 4’-phosphopantetheine = on ser side chain = vitamin B pantothenic acid
End of group is SH = how Malonyl groups are esterified

Delivers acetate (1st step) and malonate (following steps) to FaS

Shuttles growing chain through active sites during growth

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11
Q

MAT for FAS helps with what?

A

Charging of ACP

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12
Q

1 addition cycle for FAS

A

Adds two carbons
Uses 4H+ and 4e-
Releases 1CO2

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13
Q

Palmitate

A

16 C
Saturated
FAS I product

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14
Q

Palmitate production

A

8 acetyl coA + 7ATP + 14 NADPH + 14H+
—>
Palmitate + 8coA + 7ADP + 14 NADP + 6h2o

7 cycles acetylCoA carboxylase

7 cycles of condensation and reduction

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15
Q

How do liver cells Maintain high NADPH to NADP Ratio?

How do one do these things relate to FA synthesis?

A

PPP ox pathway
Malic enzyme = Malate to pyruvate

Pyruvate oxidation forms acetyl coA in mitochondrion
Also catabolism of AA carbon skeletons

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16
Q

Why is citric acid cycle important to FA?

A

Helps activate acetyl coA
Citrate production means acetyl coA —> coA-SH in mitochondrial Matrix

But
Citrate —> acetyl coA via citrate lyase in cytosol
Also produces OAA —> Malate
= RLS for FAS

17
Q

Liver, Mammary gland, kidney primary NADPH source

18
Q

Adipose tissue primary NADPH source

A

Malic enzyme

19
Q

FAS NADPH sources and ratios

A

1:1 PPP to malic enzyme

20
Q

What does citrate Allosterically activate.

What conditions encourage this?

A

Acetyl coA carboxylase

High ATP in mitochondria
High acetyl coA in mitochondria = more citrate produced

Citrate inhibits glycolysis enzymes

21
Q

What deactivates acetyl coA carboxylase?

Implications?

A

Glucagon
Epinephrine
High AMP

Palmitoyl AMP = product of Malonyl coA?

Implication: FAS is inhibited

22
Q

What does insulin activate?

A

Citrate lyase
= acetyl coA carboxylase production
= FAS activated

23
Q

Thioesterase

A

Hydrolitic
Uses H2O to break palmitate from ACP

24
Q

When FAS increased
What does this mean for E use?

A

Moving away from active E use, instead, E storage

25
What does Malonyl coA inhibit?
Fatty acid oxidation
26
Insulin and FAS
Synthesis is up Breakdown is down Insulin = in = keep E in
27
Glucagon and FA
Synthesis is down Breakdown is up Glucagon = glucose wagon = we want to use energy
28
How is FAS regulated?
NADPH availability - needed for condensation/ reduction cycle ACC inhibited by glucagon, epinephrine ACC activated by insulin and citrate
29
Elongases
Facilitate elongation…
30
Desaturation is reductive or oxidative?
Produces NADP Oxidative Carbon chains are reduced
31
How do NSAIDs inhibit inflammation
Aspirin = inhibits via acetylating essential ser residue in cyclo oexygenase h2 prostaglandin synthase (COX) Ibuprofen/ naproxen = mimic substrate structure
32
ATP cost to transport 1 mitochondrial acetyl coA
1 atp