Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.
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Transcript of Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.
![Page 1: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/1.jpg)
Chem/Biol 472 W 2011 First Exam
0123
0 11 22 33 44 55 66 77 88 99
score
Fre
qu
ency
Frequency
Average = 76.4 = B-
A = 96+A-=90-95
B+ = 85-89B= 77-84
B- = 71-76C+ = 65-70
C= 55-64
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CHAPTER 16 The Citric Acid Cycle
– Cellular respiration– Conversion of pyruvate to activated acetate – Reactions of the citric acid cycle– Regulation of the citric acid cycle– Conversion of acetate to carbohydrate precursors
in the glyoxylate cycle
Key topics:
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Only a Small Amount of Energy Available in Glucose is Captured
in Glycolysis
2G’° = -146 kJ/mol
Glycolysis
Full oxidation (+ 6 O2)
G’° = -2,840 kJ/mol6 CO2 + 6 H2O
GLUCOSE
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Cellular Respiration
• process in which cells consume O2 and produce CO2
• provides more energy (ATP) from glucose than glycolysis
• also captures energy stored in lipids and amino acids
• evolutionary origin: developed about 2.5 billion years ago
• used by animals, plants, and many microorganisms
• occurs in three major stages:
- acetyl CoA production
- acetyl CoA oxidation
- electron transfer and oxidative phosphorylation
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Respiration: Stage 1
Generates some:ATP, NADH, FADH2
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Respiration: Stage 2
Generates more NADH, FADH2 and one GTP
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Respiration: Stage 3
Makes lots of ATP
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In Eukaryotes, Citric Acid Cycle Occurs in Mitochondria
• Glycolysis occurs in the cytoplasm• Citric acid cycle occurs in the mitochondrial matrix†
• Oxidative phosphorylation occurs in the inner membrane
† Except succinate dehydrogenase, which is located in the inner membrane
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Sequence of Events in the Citric Acid Cycle
• Step 1: C-C bond formation to make citrate
• Step 2: Isomerization via dehydration, followed by
hydration
• Steps 3-4: Oxidative decarboxylations to give 2
NADH
• Step 5: Substrate-level phosphorylation to give GTP
• Step 6: Dehydrogenation to give reduced FADH2
• Step 7: Hydration
• Step 8: Dehydrogenation to give NADH
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The Citrate Synthase Reaction
• The only cycle reaction with C-C bond formation
• Essentially irreversible process
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Oxidation of -ketoglutarate
• Enzyme: -ketoglutarate dehydrogenase complex
• Similar to pyruvate dehydrogenase complex
• Same coenzymes, identical mechanisms
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The succinyl-CoA synthetase reaction.
1. A phosphoryl group replaces the CoA of succinyl-CoA bound to the enzyme, forming a high-energy acyl phosphate.
2. The succinyl phosphate donates its phosphoryl group to a His residue of the enzyme, forming a high-energy phosphohistidyl enzyme.
3. The phosphoryl group is transferred from the His residue to the terminal phosphate of GDP (or ADP), forming GTP (or ATP).
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This is a substrate-level phosphorylation. Name another one…
Phosphoglycerate kinase
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This is a reversible reaction!!! What other NTP generating reaction is irreversible?
Animal cells have another isozyme that uses ATP
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Nucleotide diphosphate kinase
• GTP + ADP ↔ ATP + GDP
ΔGo’ = 0
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The succinyl-CoA synthetase reaction. Active site of succinyl-CoA synthetase of E. coli .
The active site includes part of both the α and the β subunits.
The power helices place the partial positive charges of their helix dipoles near the phosphate group of P–His246 in the α chain, stabilizing the phosphohistidyl enzyme.
.
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Succinate Dehydrogenase
• Covalently bound FAD is reduced to FADH2
• FADH2 passes electrons to coenzyme Q
• Reduced coenzyme (QH2) can be used to make
ATP
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Hydration of Fumarate to Malate
• Fumarase is highly stereospecific• OH- adds to fumarate …
then H+ adds to the carbanion• Net effect: trans addition of water• Reversible reaction
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Not a substrate for this enzyme!Fumarase substrate
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Oxidation of Malate to Oxaloacetate
• Thermodynamically unfavorable reaction • Oxidation occurs because oxaloacetate
concentration is very low as it is continuously used
to make citrate
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Products from One Turn of the Cycle
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Net Effect of the Citric Acid Cycle
Acetyl-CoA + 3NAD+ + FAD + GDP + Pi + 2 H2O
2CO2 +3NADH + FADH2 + GTP + CoA + 3H+
• carbons of acetyl groups in acetyl-CoA are
oxidized to CO2
• electrons from this process reduce NAD+ and FAD
• one GTP is formed per cycle, this can be
converted to ATP
• intermediates in the cycle are not depleted
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COO-CH3- +CoASH CH3
C=OCoASH
When in the TCA cycle would this label be lost as CO2?
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Let's sing!!
• http://www.csulb.edu/~cohlberg/songbook.html
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Lyrics
http://books.google.com/books?id=oq9ENyL_d9YC&printsec=frontcover&source=gbs_v2_summary_r&cad=0#v=onepage&q=&f=false
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Role of the Citric Acid Cycle in Anabolism
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Anaplerotic Reactions
• these reactions replenish metabolites for the cycle
• four carbon intermediates are formed by
carboxylation of three-carbon precursors
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The role of biotin in the reaction catalyzed by pyruvate
carboxylase. Biotin is attached to the enzyme through an amide bond
with the ε-amino group of a Lys residue, forming biotinyl-enzyme.
Biotin-mediated carboxylation reactions occur in two phases,
generally catalyzed in separate active sites on the enzyme as
exemplified by the pyruvate carboxylase reaction.
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The role of biotin in the reaction catalyzed by pyruvate carboxylase. Biotin-mediated carboxylation reactions occur in two phases, generally catalyzed in separate active sites on the enzyme as exemplified by the pyruvate carboxylase reaction. In the first phase (steps 1 to 3), bicarbonate is converted to the more activated CO2, and then used to carboxylate biotin.
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The biotin acts as a carrier to transport the CO2
from one active site to another on an adjacent monomer of the tetrameric enzyme.
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In the second phase (steps 5 to 7), catalyzed in this second active site, the CO2 reacts with pyruvate to form oxaloacetate.
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Regulation of the Citric Acid Cycle
Role of citrate in glycolysis regulation?
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Figure 21-25Regulation of the citric acid cycle.
Pag
e 79
1
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Glyoxylate CycleIn plants and some other special creatures, Acetyl CoA can serve as a glucose precursor!
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2 acetyl groups enter the cycle and four carbons leave as
succinate.
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![Page 61: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/61.jpg)
![Page 62: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/62.jpg)
![Page 63: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/63.jpg)
• LEHNINGER • PRINCIPLES OF BIOCHEMISTRY
• Fifth Edition
David L. Nelson and Michael M. Cox
© 2008 W. H. Freeman and Company
CHAPTER 17Fatty Acid Catabolism
![Page 64: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/64.jpg)
![Page 65: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/65.jpg)
![Page 66: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/66.jpg)
![Page 67: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/67.jpg)
![Page 68: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/68.jpg)
![Page 69: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/69.jpg)
![Page 70: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/70.jpg)
![Page 71: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/71.jpg)
![Page 72: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/72.jpg)
![Page 73: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/73.jpg)
![Page 74: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/74.jpg)
![Page 75: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/75.jpg)
![Page 76: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/76.jpg)
![Page 77: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/77.jpg)
![Page 78: Average = 76.4 = B- A = 96+ A-=90-95 B+ = 85-89 B= 77-84 B- = 71-76 C+ = 65-70 C= 55-64.](https://reader036.fdocuments.in/reader036/viewer/2022062320/56649d4a5503460f94a2667d/html5/thumbnails/78.jpg)
“Alfonse, Biochemistry makes my head hurt!!”\