overview of metabolism

Overview of Metabolism

  • Preparation to discuss metabolism extensively in class.

  • Focus will start with catabolism and then proceed to anabolism.

General Metabolic Pathways

  • All living organisms generally share common metabolic pathways.

  • Major differences exist among different organisms but core processes are similar.

  • Metabolic pathways in bacteria often mirror those occurring in human cells.

  • Metabolism involves breaking down larger molecules into smaller ones to harvest energy for cellular function.

  • The energy produced is primarily in the form of ATP (Adenosine Triphosphate).

Byproducts of Metabolism
  • Breakdown of carbohydrates and fatty acids produces energy-depleted byproducts such as carbon dioxide (CO₂).

  • ATP has a crucial role in biosynthesis processes, e.g., using ATP to convert amino acids into proteins.

Steps of Metabolism

  • Metabolic processes utilize small steps instead of one large step to optimize energy capture.

  • This method allows for incremental energy release, which facilitates energy storage in molecules with comparable energy levels.

Metabolism Analogy: Fuel Cell vs. Fire
  • Metabolism is likened to a fuel cell instead of a fire due to distinct operational parameters:

    • Fuel cells operate at near ambient temperatures, while fires work at higher temperatures.

    • In fuel cells, oxygen does not intervene directly with fuel until later in the process, resembling cellular respiration.

Fuel Cell Example: Methanol Fuel Cell
  • Components: An anode and a cathode.

  • Anode Reaction: Methanol + Water → 1 CO₂ + 6 H⁺ + 6 e⁻

    • Electrons can perform useful work, e.g., power a vehicle or charge a battery.

  • Protons transferred to the cathode, where they and the electrons combine with oxygen to form water.

  • Oxygen is the ultimate electron acceptor, akin to its role in cellular metabolism.

Contrast with Wood Fire
  • Wood fire involves direct interaction of oxygen with wood carbohydrates, leading to immediate electron transfer and heat production without useful work.

Metabolic Anode as Citric Acid Cycle

  • The citric acid cycle utilizes acetyl CoA, a key metabolite from fats, carbohydrates, and amino acids.

  • For every acetyl CoA entering the cycle, eight electrons are harvested.

    • Electrons then enter the electron transport chain leading to oxidative phosphorylation and ATP production.

    • In the electron transport chain, oxygen acts as the terminal electron acceptor, forming water.

The Role of Electron Carriers
  • Electrons do not pass directly from the citric acid cycle to the electron transport chain.

  • They first engage with carriers, mainly NADH and FADH₂, which shuttle electrons to the chain.

  • The electron transport chain consists of series of redox reactions allowing stepwise energy extraction.

Redox Reactions

  • Fundamental to energy release in metabolism, particularly through oxidation/reduction of carbon.

  • Energy is primarily acquired through two-electron oxidation processes.

Example of Oxidation Reaction
  • Methane (CH₄) to Carbon Dioxide (CO₂) involves a series of two-electron steps:

    1. CH₄ → Methanol

    2. Methanol → Formaldehyde

    3. Formaldehyde → Formic Acid

    4. Formic Acid → CO₂

  • This process necessitates a specific ratio of oxygen per carbon throughout combustive changes.

Ratios of Oxygen to Carbon in Combustion:
  • Methane: 3 O₂ per 1 C

  • Methanol: 1.5 O₂ per 1 C

  • Formaldehyde: 1 O₂ per 1 C

  • Formic Acid: 0.5 O₂ per 1 C

  • CO₂ is fully oxidized and requires no further oxidation.

Characteristics of Oxidation in Biochemistry
  • Biochemical oxidations occur at physiological pH (around 7) and temperature (37°C).

Specific Redox Reaction Example: Ethanol to Acetaldehyde
  • Initial process involves removing a proton and two electrons from ethanol, forming a carbon-oxygen double bond in acetaldehyde.

  • Carbon becomes more oxidized, evidenced by increased carbon-oxygen bonds and decreased carbon-hydrogen bonds.

Role of Electron Transfer Agents
  • NAD⁺ (Nicotinamide adenine dinucleotide) functions primarily as an oxidizing agent in catabolic pathways.

  • NADP⁺ is differentiated with a phosphate group, serving in anabolic pathways.

  • The reduction of NAD⁺ to NADH involves adding hydride (H⁻) which reduces its positive charge.

Overall Reaction of NAD⁺ Reduction
  • Reaction: NAD⁺ + 2 e⁻ + H⁺ → NADH

Redox Pairing in Reactions
  • Ethanol oxidation is coupled with reduction of NAD⁺ to NADH and produces hydrogen ions, contributing to acidity in active muscle tissue.

Combating Potential and Gibbs Free Energy (ΔG)

  • Redox reactions can be coupled, similarly to combining exergonic and endergonic reactions.

  • Each reaction has an associated potential (E) governing spontaneity:

    • Example: NAD⁺ + 2 e⁻ → NADH potential: -0.32 V.

    • Acetaldehyde to ethanol potential: -0.2 V.

  • When combining reactions, reverse the reduction reaction to align electron transfer.

  • Example Reaction Combining:

    • Ethanol + NAD⁺ → Acetaldehyde + NADH + H⁺

Calculation of Overall Potential
  • Use combined potentials to determine spontaneity of reaction (if E is positive, reaction is spontaneous).

  • Apply Nernst equation to derive Gibbs Free Energy:
    extΔG=nFEext{ΔG} = -nFE
    where:

  • n = number of moles of electrons transferred,

  • F = Faraday's constant (96.5 kJ/V·mol),

  • E = free energy potential for the reaction.

Example Calculation for the Ethanol Reaction
  • E combined results in:
    E=0.32+0.2=0.12extVE = -0.32 + 0.2 = -0.12 ext{ V}
    extΔG=2imes96.5imes(0.12)=23extkJ/molext{ΔG} = -2 imes 96.5 imes (-0.12) = 23 ext{ kJ/mol}

  • Conclusion: a positive ΔG indicates non-spontaneity, hence a negative E becomes a catalyst for spontaneous reactions.