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Molecular Biochem final
Ch 13, 15-19
64
Biochemistry
Undergraduate 4
12/06/2010

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Term

Glycolysis step #1:

 

Definition

Glucose -----> Glucose-6-phospate

a) Mg2+ and Hexokinase

b) ATP---->ADP

Term
Glycolysis step #2:
Definition

Glucose-6-phosphate------> Fructose-6-phospate

a) Phosphoglucose isomerase (REVERSIBLE)

Term
Glycolysis step #3:
Definition

Fructose-6-phosphate ------> Fructose 1,6 bisphosphate

a) Mg2+ and Phosphofructokinase

b) ATP---> ADP

 

RATE DETERMINING

Term
Glycolysis step #5:
Definition

glyceraldehyde-3-phosphate + dihydroxyacentonephosphate ----> Triose phosphate isomerase (catalyticaly perfect enzyme)

REVERSIBLE

Term
Glycolysis steps 1-5:
Definition
Two ATP molecules are consumed.
Term
Glycolysis step #6:
Definition

Glyceraldehyde-3-phosphate ----? 1,3 Bisphosphoglycerate

a) Glyceraldehyde-3-phosphate dehydrogenase

b) Pi + NAD+ ---> NADH + H+

REVERSIBLE

Term
Glycolysis step #7:
Definition

1,3 Bisphosphoglycerate ----> 3-Phosphoglycerate

a) Phosphoglycerate kinase and Mg2+

b) ADP---->ATP

REVERSIBLE

Term
Glycolysis step #8:
Definition

3-Phosphoglycerate ----> 2-Phosphoglycerate

a) Phosphoglycerate mutase

REVERSIBLE

Term
Glycolysis step #9:
Definition

2-Phosphoglycerate ----> Phosphoenolpyruvate

a) Enolase and Mg2+

b) Yields 1 Water

REVERSIBLE

 

Term

Why there is a need to convert 2PG to PEP?

Definition

Must be converted to PEP to form a high energy intermediate that is able to synthesize. Releases a large amount of energy.

 

 

Term
Glycolysis step #10:
Definition

Phosphoenolpyruvate ----> Pyruvate

a) Mg2+ and K+ and Pyruvate Kinase

b) ADP ----> ATP

 

 

Term
What is the net production of ATP per glucose molecule?
Definition
2ATP
Term
Under aerobic conditions pyruvate is oxidized into?
Definition

CO2 and H2O.

CITRIC ACID CYCLE

Term
Under anaerobic conditions in muscle pyruvate is converted into?
Definition
Lactate.
Term
Under anaerobic conditions in yeast pyruvate is converted into?
Definition
CO2 and Ethanol.
Term
Anaerobic glycolysis in Muscle equation:
Definition
Glucose + 2ADP + 2Pi ----> 2 lactate + 2ATP + 2H2O + 2H+
Term
What is TPP?
Definition

An essential cofactor of Pyruvate decarboxylase.

Binds tightly but noncovalently.

Term
Fermentation is.....
Definition
Energetically favorable.
Term
What is the structure of PFK?
Definition
Is a tetrameric enzyme with two conformational states R and T that are at equillibrium. PFK has two binding sites and inhibitor and substrate site.
Term
Galactose is converted into?
Definition

Glucose-6-Phosphate

(4steps)

Term
Step #1 Galactose conversion:
Definition
Galactose is phophorylated at C1 by ATP in a reaction catalyzed by galactokinase.
Term
Step #2 galactose conversion:
Definition

Galactose-1- phosphate uridylyl transferase transfers the uridylyl group of UDP-glucose to galactose-1-phosphate to yield glucose-1-phosphate (G1P) and UDP-galactose by the reversible cleavage of UDP-glucose's pyrophosphoryl bond.

 

Term
Step #3 Galactose conversion:
Definition
UDP-Galactose-4-epimerase converts UDP-galactose back to UDP-glucose. This enzyme is associated NAD+, which suggests that the reaction involves the sequential oxidation and reduction of the hexose C4 atom.
Term
Step #4 Galactose conversion:
Definition
G1P is converted to the glycolytic intermediate G6P by the action of phosphoglucomutase.
Term
Conversion of Mannose into Glycolysis:
Definition

Mannose ---> Mannose-6-phosphate ---> Fructose-6-phosphate

a) ATP-->ADP (Hexokinase)

b) Phosphomannose isomerase

Term
The Pentose Phosphate Pathway:
Definition
3G6P + 6NADP+ + 3H2O ---> 6NADPH + 6H+ + 3CO2 + 2F6P + GAP
Term
What is the metabolic importance of regulating flux through the pyruvate kinase reaction?
Definition
Pyruvate kinase regulation is important for controlling the flux of metabolites, such as fructose (in liver), which enter glycolysis after the PFK step.
Term
What is the advantage of activating pyruvate kinase with fructose-1,6-bisphosphate?
Definition
FBP is the product of the reaction 3 of glycolysis, so it acts as a feed-forward activator of the enxyme that catalyzes step 10. This regulatory mechanism ensures that following 6 step in equilibrium are "pulled" into completion.
Term
Is there and energetic benefit of Glucose over Fructose?
Definition
No both produce the same amount of ATP.
Term
Is there an energetic benefit of Glucose over Mannose?
Definition
No both produce the same amount of ATP.
Term
In an erythrocyte undergoing glycolysis, what will be the effect of sudden increase in concetration of ATP?
Definition
ATP will inhibit glycolysis (PFK)
Term
In an erythrocyte undergoing glycolysis, what will be the effect of sudden increase in concetration of AMP?
Definition
AMP will stimulate glycolysis (PFK & PK)
Term
In an erythrocyte undergoing glycolysis, what will be the effect of sudden increase in concetration of G6P?
Definition
G6P will inhibit glycolysis (Hexokinase)
Term
In an erythrocyte undergoing glycolysis, what will be the effect of sudden increase in concetration of F1,6BP?
Definition
F1,6BP will stimulate glycolysis (PFK)
Term
In an erythrocyte undergoing glycolysis, what will be the effect of sudden increase in concetration of Citrate?
Definition
Citrate will inhibit glycolysis (PFK)
Term
Glycogen breakdown requires three enzymes:
Definition

a) Glycogen Phosphorylase

b) Glycogen debranching enzyme

c) Phosphoglucomutase

Term
Glycogen Phosphorylase:
Definition
Catalyzes glycogen phosphorolysis to yield glucose-1-phosphate(G1P). The enzyme releases a glucose unit only if it is at least five units away from a branch point
Term
Glycogen debranching enzyme:
Definition
Removes glycogen's branches, thereby making additional glucose residues accessible to glycogen phosphorylase.
Term
Phosphoglucomutase:
Definition
Converts G1P to G6P, which has several metabolic fates.
Term
Reacion mechanism of glycogen phosphorylase:
Definition

a) The formation of an E Pi  glycogen ternary complex.

b)Shielded oxonium ion intermediate formation.

c) Reaction of Pi with oxonium ion with overall rentention of config. about C1.

Term
Phosphoglucomutase Mechanism:
Definition

a) The OH group at C6 of G1P attacks the phosphoenzyme to form a dephosphenzyme-G1, 6P intermediate.

b) The ser OH group on the dephosphoenzyme attacks the phosphoryl group at C1 to regenerate the phosphoenzyme with the formation of G6P.

Term
Three enzymes that participate in glycogen synthesis are:
Definition

1) UDP-glucose pyrophosphorylase.

2) Glycogen synthase.

3) Glycogen branching enzyme.

Term
Glycogen Synthesis steps:
Definition

1) UDP-Glucose Pyrophosphorylase activates glucosyl units.

2) Glycogen Synthase extends glycogen chains.

3)Branching enzyme catalyses transfer and alpha 1-->4 bond formation.

Term
The mechanism of Phosphoglucomutase:
Definition

1) The OH group at C6 of G1P attacks the phosphoenzyme to form a dephosphoenzyme-G1,6P intermediate.

2) The Ser OH group on the dephosphoenzyme attacks the phosphoryl groups at the C1 to regenerate the phosphenzyme with the formation of G6P.

Term
Glycogen breakdown:
Definition
Is and exergonic process that is a reverse process that uses UTP to generate UDP-glucose intermediate.
Term
Glycogen synthesis steps:
Definition

1) UDP-glucose Pyrophosphorylase activates glucosyl units.

2) Glycogen synthase extends glycogen chains.

3) Branching enzyme catalyses transfer and alpha 1-->4 bond formation.

Term
How is a new molecule of glycogen started?
Definition
Glycogenin attaches from UDP-glucose to a Tyr residue on a protein and catalyzes extension to up to 7 glucose residues to make a primer. Glycogen synthase continues extending and branching enzymes introduces branch points.
Term
The binding of Epinephrine to liver and muscle cell receptors.......
Definition
Increases intracellular cAMP and cytosolic Ca2+ levels which promotes glycogen degradation.
Term
When glucose is plentiful.......
Definition
Insulin stimulate glucose uptake and glycogen synthesis in muscle cells.
Term
In the liver when glucose levels are high.....
Definition
Glycogen synthesis is increased.
Term
Phosphorylase Kinase....
Definition
Is activated by Ca2+ and the phosphorylation of its Alpha and Beta subunits by PKA.
Term
The conversion of pyruvate into phosphoenolpyruvate by:
Definition
Pyruvate carboxylase and PEP carboxykinase.
Term
The citric acid cycles main reason for existance is:
Definition
To break acetyl groups down by oxidation into CO2.
Term
Citric Acid cycle balanced equation:
Definition
3NAD+ + FAD + GDP + Pi + acetyl-CoA ----> 3NADH +FADH2 + GTP + CoA + 2CO2
Term
Acetyl CoA's ____ bond is high in energy.
Definition
Thioester.
Term
Oxaloacetate is:
Definition
Consumed in the first step of the citric acid cycle and regenerated in the last step of the cycle .
Term
Pyruvate Dehydrogenase Complex reaction:
Definition
Pyruvate + CoA + NAD+ ---> acetyl-CoA + CO2 + NADH
Term
TPP is....
Definition
an essential cofactor of pyruvate decarboxylase (Alcoholic fermentation in yeast)
Term
Step #1 pyruvate dehydrogenase complex:
Definition
1) Pyruvate dehydrogenase (E1), a TPP-requiring enzyme, decarboxylates pyruvate with the formation of a hydroxyethyl-TPP intermediate.
Term
Step #2 pyruvate dehydrogenase complex:
Definition
2) The hydroxyethyle group is transferred to the next enzyme, (E2) which contains a lipoamide group. The hydroxyethyl group derived from pyruvate attacks the lipoamide disulfide, and TPP is eliminated.
Term
Step #3 pyruvate dehydrogenase complex:
Definition
E2 then catalyzes a transesterification reaction in which the acetyl group is transferred to CoA, yielding acetyl-CoA and dihydrolipoamide-E2.
Term
Step #4 Pyruvate Dehydrogenase complex:
Definition
Acetyl CoA has now been formed, but the lioamide group E2 must be regenerated. E3 reoxidizes dihydrolioamide to complete the ctalytic cycle of E2. 
Term
Step #5 Pyruvate Dehydrogenase complex:
Definition
Reduced E3 is reoxidized. The Sulfhydryl groups are reoxidized by a mechanism in which FAD funnels electrons to NAD+ yielding NADH.
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