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Lecture 27 Flashcards

1
Q

Combine the terms: Catabolism, Anabolism, Reductive, Oxidative

A

Anabolism - Reductive

Catabolism - Oxidative

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2
Q

What happens to the metabolites in Catabolism?

A

They are oxidized so they lose electrons

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3
Q

What happens to the cofactors in Catabolism?

A

They are reduced (because they are oxidizing agents)

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4
Q

What are the typical cofactors in Catabolism?

A
  • NAD+

* FAD

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5
Q

What happens to metabolites in Anabolism?

A

The are Reduced (they gain electrons)

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6
Q

What happens to the cofactors in Anabolism?

A

They are oxidized (they are reducing agents)

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7
Q

What is the typical cofactor in anabolism?

A

Typically NADPH

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8
Q

What does NAD+ stand for?

A

Nicotinamide Adenine Dinucleotide

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9
Q

What role do Nucleotides play in metabolism?

A

They are electron carriers

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10
Q

What are the two nucleotide structures that act as electron carriers in metabolism?

A

NAD+ and FAD

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11
Q

What do you expect to see in dinucleotide structures?

A
  • Two phosphates
  • Two sugars
  • Two bases
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12
Q

What does FAD stand for?

A

Flavin adenine dinucleotide (FAD)

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13
Q

What portions does FAD contain?

A

A flavin portion and an adenine portion

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14
Q

What does the nitrogen base portion of the electron carrier dinucleotides allow for?

A

It enables them to undergo a reversible reduction reaction

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15
Q

Does NAD+ contain a phosphodiester?

A

No

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16
Q

Does NAD+ contain a phosphoanhydride?

A

Yes

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17
Q

What links nucleotides in nucleic acids?

A

Phosphodiester bonds

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18
Q

What links nucleotides in NAD+ and FAD?

A

Phosphoanhydride bonds

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19
Q

Why is there no sense of direction in NAD+?

A

Because the phosphoanhydride connects to both 5’ groups on the ribose instead of the 5’ and the 3’

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20
Q

What is the bottom part of NAD+ made of?

A

Adenine, a phosphate and ribose

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21
Q

What is the top part of NAD+ made of?

A

A phosphate, a ribose, a nitrogen containing heterocyclic aromatic base structure

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22
Q

Where does reduction occur in NAD+?

A

At the nicotinamide base

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23
Q

What does the reduction process of NAD+ ential?

A

Accepting an H+ and 2e which gets rid of one of the double bonds and protonates the carbon 4 reducing NAD+ to NADH

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24
Q

Why isn’t the other nitrogenous base (the one thats not adenine) a pyrimidine?

A

Because it doesn’t have a second nitrogen

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25
What is it called after NAD+ is reduced?
It it called NADH
26
What is the difference between NAD+ and NADP+?
NADP has an additional phosphate at the 2' position within the adenosine
27
How does the additional phosphate on NADP affect the reduction process?
It does not because is is on the ribose sugar
28
Why is NAD+ named NAD+?
Because it carries a positive charge in the net ring portion of the structure, it is overall negative though
29
What is the bottom portion of FAD made of?
Adenine, ribose, and a phosphate
30
What does the top part of FAD have?
A ribose derivative, a phosphate, aromatic nitrogen containing heterocyclic base (flavin)
31
What is reduced in FAD?
The Flavin ring
32
What does reduction of FAD entail?
Two H+ and 2e
33
What is NAD+ typically involved in?
C-O bond oxidation
34
What is the reduced form of FAD?
FADH2 or FMNH2
35
What is FAD typically involved in?
In C-C bond oxidation
36
What connects the nucleotides to each other in FAD?
A phosphoanhydride bond
37
What is required to reduce NAD+?
* H+ | * 2e
38
What is required to reduce NADP+?
* 2H+ | * 2e
39
What is needed to reduce FAD?
* 2H+ | * 2e-
40
What are the products of reduction of NAD+?
NADH and H+
41
What are the products of reduction of NADP+?
NADPH and H+
42
What are the productions of reduction of FAD?
FADH2
43
What is the difference in action between NAD+, NADP+ and FAD/FADH2?
Typically NAD+ and NADP+ are cosubstrates so they dissociated after the reaction whereas FAD is a prosthetic group so it remains even after the reaction
44
What is a consequence of FADH2 being a prosthetic group?
It needs to be reoxidized back into FAD for the next enzyme cycle to occur
45
What can be considered high energy molecules?
GTP and GDP because of the phosphoanhydride bond
46
What characteristics do anabolic pathways do?
* They generate macromolecules from simpler ones | * They generate oxidized enzyme cofactors
47
What is associated with a large free energy change in ATP?
The phosphoanhydride bonds
48
How many kj/mol does hydrolysis of the phosphoanhydride bond of ATP release?
-32kJ/mol
49
How much energy does making ATP require?
+32 kJ/mol
50
Why is there so much energy from releasing a phosphoanhydride bond?
* Decreases electrostatic repulsion * Resonance stabilization * Solvation effects
51
How is does the removal of a phosphate group from ATP affect electrostatic repulsion?
It decreases electrostatic repulsion of the ATP molecule
52
What is the charge density of phosphoanhydride bonds?
They have a very large negative charge density
53
What is the resonance stabilization of ATP vs HPO4?
HPO4 has a greater degree of resonance stabilization than when on the ATP molecule
54
How is solvation affected by the hydrolysis of the phosphoanhydride bond of ATP?
There is a higher degree of solvation og HPO4
55
What are Thioesters?
Higher energy compounds similar to esters but with no e delocalization
56
What happens if we decrease the free energy of products?
Then we increase the free energy change associated with the process
57
How does resonance affect the energy of substrates?
Increased resonance decreases the energy of substrates
58
What does a hydrolyzed ester yield?
A carboxyl and an alcohol
59
What does hydrolysis of a Thioester yield?
A carboxylate and a thiol
60
What is the difference in the free energy of an ester and the free energy of a thioester?
The free energy released from a thioester is more negative than the free energy released from an ester
61
Why is the free energy released from a thioester more negative than the free energy released from an ester?
Because Esters have a lower starting energy and are more resonance stabilized
62
What is the value of the free energy change of thioesters?
-32kJ/mol
63
By what process is ATP generated by?
Catabolism
64
What is ATP used in?
Driving unfavorable reactions Movement (muscle, flagella) Primary active transport (ion pumping)
65
What is coupling of a reaction?
When a reaction with an overall unfavorable free energy change (𝛥G > 0) can occur when another favorable reaction (𝛥G < 0) occurs in concert and have an overall 𝛥G < 0

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