BioChem Exam #4 Flashcards
What are the overall products of Glycolysis?
- 2 ATP;
- 2 NADH + 2H+
- 2 Pyruvate
What is the purpose of Glycolysis?
- Produce ATP;
- Provide building blocks for synthetic purposes
What are the 2 pathways that Pyruvate can take after glycolysis?
- ANAEROBIC to Lactic Acid or Alcoholic Fermentation;
- AEROBIC to the Citric Acid Cycle
What is Lactic Acid Fermentation?
- ANAEROBIC;
- Oxidation Reduction Rxn single conversion from pyruvate to lactic acid;
- USES 2 NADH + 2H+ to produce Lactic acid and 2NAD+;
- 2C pyruvate to 3C lactic acid
What is the enzyme for Lactic Acid Fermentation?
Lactate Dehydrogenase =
- Give’s pyruvate electrons (reduce) to REMAKE NAD+
- NADH is oxidized;
- Found in Muscle Tissue and Lactic Acid bacteria
What is Alcoholic Fermentation?
- ANAEROBIC;
- 2 step process that generates 2CO2 and 2 ethanol and 2 NAD+ from pyruvate;
- Yeast in bread and alcohol
What is the first step of Alcoholic Fermentation?
- Pyruvate DECARBOXYLASE Rxn;
- Converts Pyruvate (3C) to acetylaldehyde (2C) with CO2 as a byproduct
What is the second step of Alcoholic Fermentation?
- ALCOHOL DEHYDROGENASE;
- Oxidation reduction rxn of 2 acetylaldehye to 2 ethanol and 2NAD+;
- Reduces the acetylaldehye (add electrons) and oxidize NAHD + H+ (lose electrons) to make ethanol and REMAKE NAD+
What is the purpose of both methods of Fermentation?
- Regeneration of NAD+ so that it can return to glycolysis and keep it going;
- Other products are TOXIC!
How much ATP is made after both glycolysis and fermentation?
- STILL only 2 ATP that came from glycolysis;
- Fermentation makes NO energy
What is the TCA (Citric Acid Cycle)?
- The AEROBIC, ENERGY generating of pyruvate;
- Occurs after glycolysis in the presence of Oxygen
What are the products of the TCA cycle?
- GTP (analogous to ATP);
- NADH + H+
- 6 CO2;
- DOES NOT remake NAD+
What is the purpose of the TCA cycle?
- Complete breakdown of glucose to CO2;
- Produce energy-containing molecules (GTP);
- Provide building blocks for other pathways (NADH)
What happens in AEROBIC respiration after the TCA cycle?
- The (NAHD + H+) takes its extra electron to the electron transport chain to REMAKE NAD+;
- Electrons are then passed down the chain
What happens with the Electron Transport Chain (ETC)?
- The energy from the electrons being passed down the down, drive the synthesis of ATP (energy);
- Electrons themselves (and protons) are picked up by Oxygen and H2O is produced as a waste product
What is the purpose of the ETC?
- Regenerate NAD+;
- Drive ATP synthesis
How many ATP are produced after AEROBIC Respiration (Glycolysis, TCA, and ETC)?
-36-38 total ATP per glucose molecule
What are the WASTE products of AEROBIC respiration?
- Lactic acid
- Ethanol
- Gets rid of excess electrons
What is the WASTER product of AEROBIC respiration?
- H2O
* Gets rid of excess electrons
What are the final ELECTRON ACCEPTOR for ANAEROBIC respiration?
- Pyruvate;
- Acetaldehyde
What is the final ELECTRON ACCEPTOR for AEROBIC respiration?
-Oxygen
Why does NAD+ need to be regenerate so that Glycolysis can keep going?
- NAD+ needs to be in EXCESS to drive the generation of ATP forward and take on electrons (be reduced);
- WIthout enough, the Glyceraldehyde-3-PO4 dehydrogenase rxn will stop and glycolysis will stop
Why would not having enough NAD+ stop the GLyceraldehyde-3-PO$ dehydrogenase rxn?
- This reaction is a Oxidation-Reduction ruxn;
- NAD+ is reduced so that Glyceraldehyde-3-PO4 can be oxidized to Glycerate-3-PO4 which will then generate ATP;
- Without this redox, glycolysis can’t continue and no ATP are created
Why can’t the brain run off of ANAEROBIC pathways?
- Can’t handle the toxic products (ethanol and lactic acid);
- Needs high amount of energy constantly;
- Cells do not have fermenting capabilities
What is the Pasteur Effect?
- Breakdown of glucose in the PRESENCE of OXYGEN decreases drastically in yeast cells;
- Aerobically produce so much energy per glucose molecule, so need Fewer glucose to get the same/more energy;
- Yeast cells always need energy at a constant rate so energy quickly becomes excess with oxygen
Where does the TCA cycle take place?
-Mitochondria MATRIX (eukaryotic cells)
What are the components of the Mitochondria?
- Inner membrane (very selective);
- Outer membrane (not selective);
- Cristae (folds of the inner membrane);
- Intermembrane space
- MATRIX is enclosed by the inner membrane
The inner membrane of mitochondria is NOT permeable to what molecules?
- Sugars;
- NAD+, NADH;
- H+ (protons_
What is found in the matrix to allows for aerobic respiration and utilization of pyruvate?
- Matrix contains soluble enzymes that catalyze the oxidation of pyruvate;
- ATP synthase is found in the inner membrane which allows for the ultimate production of ATP through the ETC
How does pyruvate get into the mitochondria?
-Requires a transport mechanism due to selectivity of the membranes;
(Glycolysis had occurred in the cytoplasm)
How does Pyruvate enter into the TCA Cycle?
- ACTIVATED to Acetyl-CoA;
- Oxidative Decarboxylation rxn;
- Enzyme = Pyruvate Dehydrogenase Complex
How does the Oxidative Decarboxylation Rxn of PYRUVATE to ACETYL-CoA work?
- Pyruvate (3C) is oxidized (lose electrons);
- Then reacts with Coenzyme-A-SH;
- NAD+ is reduced (gains electrons) and produces NADH and H+;
- CO2 is also generated and removed from Pyruvate;
- Acetyl-CoA (2C) is produced
What are the rxn characteristics of the activation of Pyruvate to Acetyl-Co-A?
- Oxidative Decarboxylation Rxn (pyruvate oxidized, loses CO2);
- Irreversible, spontaneous;
- Large, negative delta G;
- Activation step!;
- Enzyme complex is controlled
What is the Pyruvate Dehydrogenase Complex?
- GROUP of soluble enzymes that ALWAYS work together in succession to turn pyruvate into acetyl-cowa;
- All-or-nothing, permanently linked;
- Highly efficient;
- Very large complex;
- All components are separate, but work hand-in-hand passing from one to the next;
How many catalytic enzymes are apart of the Pyruvate Dehydrogenase Complex?
- E1 (alpha, beta dimer, surround the core)
- E2 (forms the core);
- E3 ( dimer, “the glue between the others)
What are the two forms of Cofactors?
- Prosthetic group (permanently attached to enzymes)
- Coenzymes (come in and out of attachment as needed)
What is the cofactor for E1?
-TPP (thiamine pyrophosphate) = PROSTHETIC;
Need Thiamine to produce
What are the cofactors for E2?
- Lipoic acid = PROSTHETIC;
- CoA-SH = COENZYME (need pantothenic acid to produce)
What are the cofactors for E3?
- FAD = PROSTHETIC (need riboflavin);
- NAD+ = COENZYME (need niacin)
What are the REGULATORY components of the Pyruvate Dehydrogenase Complex?
- Pyruvate dehydrogenase kinase;
- Pyruvate dehydrogenase phosphate phosphatase;
- REGULATE E1
Why is the production of Acetyl-Co-A controlled?
-Because it is a BRANCH POINT compound for several pathways
What types of enzyme control regulate the Pyruvate Dehydrogenase Complex?
- Allosteric inhibitors (products);
- Location/Degree of organization in the cell (Mitochondria/All or nothingMulti-enzyme complex);
- Covalent modification (adding/removing PO4 to E1)
How is the Complex regulated ALLOSTERICALLY?
- E2 is INHIBITED by AcCoA;
- E3 is INHIBITED by NADH
- Regulated by the PRODUCTS of that rxn, b/c it is a branch point!
How is the Complex regulated by COVALENT MODIFICATION at E1?
- E1 ALONE is ACTIVE;
- Adding PO4 makes E1 INACTIVE;
- Reversible by another enzyme;
- Totally turns E1 OFF (typical covalent modification)
How is PO4 added to E1 to make it INACTIVE?
- Enzyme = Pyruvate Dehydrogenase Kinase removes a PO4 (Pi, inorganic phosphate) from ATP and ADDS it to E1 and leaving ADP;
- Allosteric control of Kinase
What is the INACTIVE form of E1?
-Pyruvate Dehydrogenase Phosphate
How is E1 REACTIVATED?
- Enzyme = Pyruvate Dehydrogenase Phosphate Phosphatase;
- PO4 (Pi) is REMOVED creating a free inorganic phosphate (Pi) and ACTIVE E1;
- Allosteric control of Phosphatase
How is Pyruvate Dehydrogenase KINASE (regulator enzyme) controlled?
- Allosteric;
- ACTIVATED by Acetyl-CoA and NADH;
- INHIBITED by CoA and NAD+
How is Pyruvate Dehydrogenase Phosphate PHOSPHATASE (regulator enzyme) controlled?
- Allosteric;
- ACTIVATED by ADP (low energy)
Why do the INHIBITORS of E2 and E3 (Acetyl-CoA and NADH) ACTIVATE the Kinase regulator?
-When the complex needs to be turned OFF, Acetyl-CoA and NADH are present to both STOP E2 and E3, but also activate pyruvate dehydrogenase Kinase, which then STOPS E1
Why is the Pyruvate Dehydrogenase Complex so carefully controlled?
- Because creating Acetyl-CoA from pyruvate is the commitment step AWAY from any glucose synthesis or glycolysis!;
- NO more Carbons are available for net Carb synthesis;
- This can only occur when the brain is happy and has adequate glucose to function
Why is the conversion from pyruvate to acetyl-coA important?
- Irreversible, spontaneous, large neg. delta G reaction;
- Activation step for several pathways;
- Commitment step to make Acetyl-CoA = NO MORE CARBS
Where else can Acetyl-CoA come from?
- Carbs to pyruvate to Ac-CoA;
- Breakdown of some amino acids (can be used for energy, but not as glucose);
- Fatty acid breakdown
What else can Acetyl-CoA be used to make?
- Enter TCA cycle to make energy;
- Fatty acid synthesis;
- Some amino acid synthesis;
- Synthesis of some steroids and other lipids
What are the roles of the TCA cycle?
- Oxidized acetyl (Carbon) group to CO2 and H2O;
- Produce biosynthetic intermediates (building blocks for other paths);
- Recover energy as NADH, FADH2, and GTP (ATP)
How is energy recovered through the TCA by NADH and FADH2?
-They are oxidized and give electrons the the ETC where oxidative phosphorylation can create ATP from the electrons energy
What is the FIRST step with Acetyl-CoA to start the TCA cycle?
- 2C Acetyl-CoA combines with 4C oaxaloacetate (OAA) to create a 6C Citrate;
- Bond between the Carbonyl C of OAA and the activated CH3 of Ac-CoA;
- Enzyme = Citrate Synthase;
- Large, neg. delta G rxn
How the small CH3 group on Ac-CoA made reactive?
-The high energy contained in the THIOESTER bond with Sulfur and Coenzyme A n the Ac-CoA withdraws electrons making it more reactive
What are the 2 roles of Citrate Synthase?
- Removes the SH-CoA from the acetyl group of Acetyl-CoA;
- And then combines the 2C acetyl group with the 4C OAA;
- Makes Citrate (6C)
How is the CItrate Synthase Reaction controlled?
- Commitment to TCA!;
1. Allosteric;
2. Substrate conc. of OAA
How is the Citrate Synthase Rxn controlled Allosterically?
-INHIBITED by ATP, NADH, Succinyl-CoA
How the Citrate Synthase Rxn controlled by Substrate conc OAA?
- The conc. of OAA is VERY LOW, so any change in the conc. at ALL causes as Large change;
- Not much to work with in the first place
Why does the Citrate Synthase Rxn release so much energy as heat?
- The large negative delta G value is NOT stored as energy, but it needed to pull the cycle around and allow it to continue;
- The delta G value to convert from L-malate to OAA is very positive and needs the extra energy to occur
- DIRECT ENERGY COUPLING REACTION
What is CITRATE (6C) converted to?
- ISOCITRATE (6C);
- Undergoes a rearrangement of an (-OH) group from the 3rd to 4th carbon
How is Citrate converted to Isocitrate?
Enzyme = ACONITASE:
- Rearrangement occurs by the removal of an H2O that swings around the molecule and is put back on in the backwards position with the help of IRON (Ferris Wheel mechanism);
- Positive delta G, so PREFERES THE REVERSE rxn
Why does Aconitase always move the -OH from the 3rd to the 4th carbon?
- Aconitase is a STEREOSPECIFIC enzyme;
- Even though Carbon of citrate was NOT chiral, the stereospecifcity of Aconitase always moves the -OH down from the 3rd to 4th carbons
What is ISOCITRATE (6C) converted to?
- ALPHA KETOGLUTARATE (5C);
- Dehydrogenase and Oxidative decarboxylation rxn that REMOVES CO2 and uses NAD+ to remove electrons (dehydrogenase or redox rxn);
- Products are CO2 and (NADH + H+)
How is Isocitrate converted to Alpha-KG?
Enzyme = ISOCITRATE DEHYDROGENASE
- Decarboxylation removal of CO2 to convert 6C to 5C;
- Reduction of NAD+ to NADH + H+ to remove electrons (;
- IRREVERSIBLE;
- Allosterically increased by ADP/NAD+;
- Allosterically inhibited by ATP/NADH
What is Alpha-KG converted to?
- SUCCINYL-CoA (4C);
- Removal of CO2 (oxidative decarboxylation) and electrons (dehydrogenase) to ADD CoA-SH
How is Alpha-KG converted to Succinyl-CoA?
Enzyme = Alpha-KG dehydrogenase complex;
- Activation step to create a high energy THIOESTER bond between Carbon and Sulfur of Coenzyme A;
- Reduction reaction to remove electrons with NAD+ to (NADH + H+)-
- Decarboxylation to remove CO2 makes 5C (KG) into 4C;
- IRREVERSIBLE rxn
How is the Alpha-KG dehydrogenase complex controlled?
- ALLOSTERICALLY = increased by ADP/NAD+; inhibited by ATP/NADH;
- LOCATION or ORGANIZATION of the complex (all or nothing);
- NO covalent modification
What is the purpose of creating the thioester bond of Succinyl-CoA?
-Creates a HIGH ENERGY bond creating storage in the substrate (S-CoA) for the next reaction to be able to generate energy