What is the reaction potential for oxidation of NADH (for completely passing electrons from NADH to O2) with units? 2. What is the reaction potential for oxidation of FADH2 (from FADH2 to O2) with units? 3. Which reaction has a more negative deltaG?
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What is the reaction potential for oxidation of NADH (for completely passing electrons from NADH to O2) with units?
2. What is the reaction potential for oxidation of FADH2 (from FADH2 to O2) with units?
3. Which reaction has a more negative deltaG?
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- Acetaldehyde + NADH + H+ → Ethanol + NAD+ How is the inhibition constant for this gotten? Determine the inhibition constant(s) of AMP?Shown below are reduction potentials for four half-reactions. Which of the coupled reactions is favorable? (Note that for Cytochrome c you must multiply the reduction potential by 2 for each coupled reaction because only one electron is involved) a) 2 Cytochrome c (Fe3+) + H2O ó 2 Cytochrome c (Fe2+) + O2 b) NADH + Succinate- ó NAD+ + Fumarate- c) Fumarate- + H2O ó Succinate- + O2 d) All of the aboveOne process catalyzed by NADHNADH dehydrogenase is NADH+H^++ubiquinone ↽−−⇀ NAD+ubiquinolNADH+H^++ubiquinone ↽−−⇀ NAD^++ubiquinol The standard reduction potentials for the half‑reactions are given in the table. Oxidant Reductant ?′0 ubiquinone+2H++2e−ubiquinone+2H++2e^− ubiquinolubiquinol 0.045 NAD^++H^++2e−NAD^++H^++2e^− NADHNADH –0.32 Calculate Δ?′0 for the reaction as shown. Δ?′0=____(V) Calculate Δ?′0 . Δ?′0=____(kJ/mol)
- Consider the two half-reactions below and their standard reduction potentials. NAD+ + H+ + 2e → NADH Elo= -0.32 V a-Ketoglutarate + CO₂ + 2H+ + 2e → Isocitrate E' = -0.38 V (a) What is AE" for the spontaneous redox reaction that is, the reaction that actually occurs under standard biochemical conditions (pH 7)? (b) Which of the following statements are correct under standard biochemical conditions? i. The concentration of H+ is 1.0 M. ii. The reaction NAD+ + Isocitrate → NADH + H+ + a-Ketoglutarate + CO₂ is favor- able. iii. NAD+ accepts electrons from isocitrate. iv. The NAD → NADH reaction actually occurs in reverse. The a-ketoglutarate → isocitrate reaction occurs as written. (c) Calculate AG" for the reaction in (a). (pH 7, 25°C, pressure, 1 atm.) (d) Suppose that the actual conditions are T = 25°C, pH = 7, CO₂ = 1 atm, [a-Ketoglutarate] 10 mM, [NAD+] = 2.5 mM, and [NADH] = 0.5 mM. PAR = 2 mM, [Isocitrate] DE What is the value of AG under those conditions? (Hints: pH 7 is already…3. Pyrozole has been proposed as a possible nontoxic inhibitor of LADH-catalyzed ethanol oxidation. Its kinetics have been studied and, in 2 separate experiments, the velocity of the reaction was measured as a function of [C₂H5OH] and of [NAD+]. The data is given in the tables below. [C₂H5OH] varies, [LADH]= 4µg/ml, [NAD+] = 350 µM, pH=7.4, 23.5C [C₂H5OH] Vo (relative units) Vo (relative units) 1x10-5 M pyrazole M No pyrazole 2.1 1.8 1.5 1.35 0.008 0.002 0.001 0.00067 Vo (relative units) No pyrazole 0.00011 1.7 0.000056 1.4 0.000033 1.3 0..000017 0.95 1.7 1.0 [NAD+] varies, [LADH]= 4µg/ml, [C₂H5OH]= 5 mM, pH=7.4, 23.5C [NAD+] Vo (relative units) 4x10-5 M pyrazole 0.69 0.52 0.85 0.71 0.63 0.47 a. Plot the data as Lineweaver-Burke plots on two separate graphs. b. Determine the Km values for [C₂H5OH] and of [NAD*]. (You can't find Vmax because the exact units of Vo are not provided) c. What type of inhibition is exhibited by pyrazole against C₂H5OH is a substrate? Describe what is going…Given what you know about the involvement of nicotinamide nucleotides inoxidative and reductive metabolic reactions, predict whether the followingintracellular concentration ratios should be 1, > 1, or < 1. Explain youranswers.(a) [NAD+] >[NADH](b) [NADP+] >[NADPH](c) Since NAD+ and NADP+ are essentially equivalent in their tendency to attract electrons, discuss how the two concentration ratios might bemaintained inside cells at greatly differing values.
- The inhibitor X prevents coenzyme Q (Q) from participating in electron transfer in the electrontransport chain.(a) Will the presence of X prevent electrons from N ADH from passing through the electron trans-port chain? Explain why or why not.(b) Compound Y is a non-physiological reducing agent capable of directly reducing cytochromec1 in Complex III. Would oxygen consumption resume upon the addition of compound Y tomitochondria inhibited by inhibitor X? Be sure to explain your answer.By what factor is sample A2 more concentrated than sample A1?6. Malate dehydrogenase catalyzes the following reversible reaction: COO- HO-C-H CH₂ COO™ L-Malate NAD+ y malate NADH + H+ dehydrogenase COO- 0=C CH₂ COO™ Oxaloacetate AG'° = 29.7 kJ/mol Malate + NAD+→NADH + H+ + oxaloacetate Calculate AG" and the ratio or products and reactants for the malate dehydrogenase reaction to proceed from left to right as shown. (The Faraday constant. 3, is 96.48 kJ/V-mol; RT(37°C)= 2.58kJ/mol) Steps: 1. Explain how you determined which molecule is an electron donor Malate and which is an acceptor NAD*. -2- 2. Calculate AED (write equation, then show calculations, for standard reduction potentials (E_values) see table in the posted lecture) 3. Calculate AG (write equation, then show calculations) 4. Calculate the ratio of products and reactants needed to for Malate + NAD+→→NADH + H+ + oxaloacetate reaction to proceed forward (write equation, then show calculations)
- The values of the reduction potential (Eº') of the conjugated redox pairs NAD+/NADH and pyruvate / lactate are -0'32 V and -0'19 V respectively. a) Which of the two conjugated pairs has a greater tendency to lose electrons? Reason for it. b) What is the strongest oxidizing agent? Reason for it. c) If we start with 1M concentrations of each reagent and product at pH 7.0 in which sense the reaction will pass pyruvate + NADH + H+ ⇄ lactate + NAD+ d) What is the standard free energy variation (ΔGº’ at 25ºC) for the conversion of pyruvate to lactate? e) What is the equilibrium constant of this reaction?The enzyme lactate dehydrogenase catalyzes the reversible reaction lactate (CH3 CHOHCOO )+NAD* рyruvate (CH3 COCOO) + NADH + H+ Given the standard reduction potentials CH3 СОСОО + 2H+ + 2е CH3 CHОНСО" E°'= -0. 185 V NADŤ + H+ + 2e- → NADH = -0. 320 V E°' would you expect the reaction to be spontaneous in the forward or reverse direction under biochemical standard state conditions? How could you change the reaction conditions to force the reaction to be spontaneous in the opposite direction? Please explain your answer.Below are the reduction reactions for oxygen and FAD. ½202 + 2e + 2H+ → H20 E°' = 0.83 V FAD + 2e + 2H* → FADH2 E" = -0.22 V What is the potential (E") for the oxidation of FADH by oxygen? What is the AG®' for the oxidation of FADH, by oxygen? If we assume that the pumping of protons in conjunction with the oxidation of FADH, requires 120 kJ, what percentage of the energy from FADH oxidation is stored in the proton gradient (think about how many protons are pumped when FADH, transfers electrons to oxygen)?
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