Bioenergetics and Thermodynamics

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Thermodynamic Principles - Energy's Ebb & Flow

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ATP - Cellular Power Coin

ATP molecule structure with high-energy bonds

  • Adenosine Triphosphate (ATP): Universal energy currency.
    • Structure: Adenine base, Ribose sugar, 3 Phosphate groups ($\alpha, \beta, \gamma$).
    • High-energy bonds: Two phosphoanhydride bonds (between $\gamma-\beta$ & $\beta-\alpha$ P).
  • Hydrolysis & Energy Release:
    • $ATP \rightarrow ADP + P_i$; $\Delta G \approx \text{-30.5 kJ/mol}$ ($\text{-7.3 kcal/mol}$).
    • $ATP \rightarrow AMP + PP_i$; $\Delta G \approx \text{-45.6 kJ/mol}$ ($\text{-10.9 kcal/mol}$).
    • $PP_i$ hydrolysis to $2 P_i$ further drives reactions.
  • Key Roles: Powers biosynthesis, active transport, muscle contraction.
  • Major Synthesis Pathways:
    • Substrate-level phosphorylation.
    • Oxidative phosphorylation (primary).
  • Regulation: ATP/ADP ratio influences metabolic flux.

⭐ A resting human turns over their body weight in ATP daily (approx. 50-75 kg).

Redox & Electron Carriers - Energy Baton Pass

  • Redox: Coupled reactions.
    • Oxidation: Loss of e⁻ (LEO). Oxidizing agent accepts e⁻.
    • Reduction: Gain of e⁻ (GER). Reducing agent donates e⁻.
  • Redox Potential ($E_0'$): Measure of e⁻ affinity.
    • e⁻ flow: more negative $E_0'$ → more positive $E_0'$.
    • $\Delta G^{0'} = -nF\Delta E_0'$.
  • Key Electron Carriers:
    • NAD⁺/NADH: Carries 2e⁻, 1H⁺. From Niacin (B3). For ATP synthesis.
    • NADP⁺/NADPH: Anabolic reactions.
    • FAD/FADH₂: Carries 2e⁻, 2H⁺. From Riboflavin (B2).
    • FMN: Similar to FAD (Flavin Mononucleotide).
    • Coenzyme Q (Ubiquinone): Lipid-soluble.
    • Cytochromes: Heme proteins (Fe²⁺↔Fe³⁺). Cellular Respiration Pathways

⭐ NADH generates approx. 2.5 ATP; FADH₂ generates approx. 1.5 ATP via oxidative phosphorylation. 📌 LEO says GER: Loss Electrons Oxidation, Gain Electrons Reduction.

ATP Synthesis Mechanisms - Factory Blueprints

  • Two main ATP factories:

    • Substrate-Level Phosphorylation (SLP)
    • Oxidative Phosphorylation (OxPhos)
  • Substrate-Level Phosphorylation (SLP):

    • Direct $P_i$ transfer to ADP from high-energy substrate.
    • Enzymes: Kinases.
    • Locations: Cytosol (Glycolysis), Mitochondrial matrix (TCA cycle).
    • Key steps:
      • 1,3-BPG $\rightarrow$ 3-PG
      • PEP $\rightarrow$ Pyruvate
      • Succinyl CoA $\rightarrow$ Succinate (GTP mediated)
    • Rapid, O₂ not directly required.
  • Oxidative Phosphorylation (OxPhos):

    • Major ATP yield; Inner mitochondrial membrane.
    • ETC: e⁻ flow (NADH, FADH₂) pumps H⁺ $\rightarrow$ proton motive force (PMF).
    • ATP Synthase (Complex V) uses PMF for ATP synthesis.
    • O₂: Final electron acceptor.
    • Yield: NADH ≈ 2.5 ATP; FADH₂ ≈ 1.5 ATP (P/O). ATP synthesis via oxidative phosphorylation in mitochondria

⭐ Uncouplers (DNP, Aspirin, Thermogenin) dissipate H⁺ gradient: ATP ↓, O₂ use ↑, heat ↑.

High‑Yield Points - ⚡ Biggest Takeaways

  • Gibbs Free Energy (ΔG) dictates reaction spontaneity: negative ΔG for exergonic (releases energy), positive for endergonic (requires energy).
  • ATP is the universal energy currency; its hydrolysis to ADP + Pi releases approx. -7.3 kcal/mol (or -30.5 kJ/mol).
  • Standard Free Energy Change (ΔG°') is defined at pH 7, 25°C (298K), and 1M concentrations for all reactants and products.
  • Coupled reactions enable thermodynamically unfavorable (endergonic) reactions to proceed by linking them to highly favorable (exergonic) reactions, often ATP hydrolysis.
  • Electrons spontaneously flow from substances with a more negative reduction potential (E°') to those with a more positive E°'.
  • Key high-energy phosphate compounds like phosphoenolpyruvate (PEP) and 1,3-bisphosphoglycerate (1,3-BPG) possess a higher phosphate transfer potential than ATP, meaning their hydrolysis releases more energy.
  • The actual free energy change (ΔG) depends on ΔG°' and actual cellular concentrations of reactants and products (related by ΔG = ΔG°' + RT ln Q).

Practice Questions: Bioenergetics and Thermodynamics

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Which factor predominantly influences the rightward shift of the oxygen dissociation curve?

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Flashcards: Bioenergetics and Thermodynamics

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An _____ bond is present between two phosphate groups.

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An _____ bond is present between two phosphate groups.

acid anhydride

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