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Biological Chemistry II
Table of Contents
Unit 1 Overview: Metabolism and Bioenergetics
1.1 Overview of metabolism
1.2 Laws of thermodynamics in biological systems
1.3 Free energy and chemical reactions
1.4 High-energy compounds: ATP and phosphorylation
1.5 Coupled reactions and energy transfer
1.6 Redox reactions in living systems

Redox reactions are the unsung heroes of life, powering everything from breathing to thinking. They involve electron swapping between molecules, driving energy production and countless biological processes. Without them, we'd be toast.

In living systems, redox reactions are like a cellular dance party. Molecules like NAD+ and FAD keep the groove going, shuttling electrons around to power metabolism. The electron transport chain is the DJ, pumping out ATP to keep the party rocking.

Oxidation and Reduction in Biology

Fundamental Concepts of Redox Reactions

  • Oxidation involves loss of electrons or hydrogen atoms from a molecule or increased oxidation state of an atom
  • Reduction entails gain of electrons or hydrogen atoms by a molecule or decreased oxidation state of an atom
  • Redox reactions couple oxidation of one molecule (electron donor) with reduction of another (electron acceptor)
  • Electron transfer often paired with proton (H+ ion) transfer maintains charge balance
  • Redox reactions underpin key biological processes (cellular respiration, photosynthesis, metabolic pathways)
  • Reduction potentials of molecules influence direction and extent of biological redox reactions
  • Oxidoreductase enzymes catalyze biological redox reactions facilitating electron transfer

Examples and Applications

  • Cellular respiration oxidizes glucose to CO2 while reducing O2 to H2O
  • Photosynthesis reduces CO2 to glucose while oxidizing H2O to O2
  • Cytochrome c oxidase in mitochondria reduces O2 to H2O during cellular respiration
  • Alcohol dehydrogenase oxidizes ethanol to acetaldehyde in liver cells for detoxification
  • NADPH oxidase in immune cells produces reactive oxygen species to combat pathogens

NAD+ and FAD in Redox Reactions

Structure and Function of NAD+ and FAD

  • Nicotinamide adenine dinucleotide (NAD+) and flavin adenine dinucleotide (FAD) act as essential electron-carrying coenzymes
  • NAD+ accepts electrons and proton forming NADH
  • FAD accepts two electrons and two protons forming FADH2
  • Participate in numerous metabolic pathways (glycolysis, citric acid cycle, electron transport chain)
  • Transfer electrons from reduced substrates to electron transport chain for ATP production
  • NAD+/NADH and FAD/FADH2 ratios regulate metabolic processes and maintain cellular redox balance
  • Function as substrate molecules for certain enzymes beyond electron carrier role

Regeneration and Metabolic Importance

  • Regeneration of NAD+ and FAD from reduced forms maintains continuity of metabolic processes
  • NAD+ regenerated through lactate dehydrogenase in anaerobic glycolysis
  • FAD regenerated through succinate dehydrogenase in citric acid cycle
  • Malate-aspartate shuttle regenerates NAD+ in cytosol during aerobic metabolism
  • Glycerol-3-phosphate shuttle regenerates FAD in mitochondrial matrix
  • NAD+ involved in DNA repair processes through PARP enzymes
  • NADPH crucial for biosynthetic reactions and antioxidant defense mechanisms

Electron Transport Chain for Energy

Components and Mechanism

  • Electron transport chain (ETC) comprises protein complexes in inner mitochondrial membrane (eukaryotes) or plasma membrane (prokaryotes)
  • Four main protein complexes (I, II, III, IV) and two mobile electron carriers (ubiquinone, cytochrome c) form ETC
  • Electrons from NADH and FADH2 flow through ETC complexes releasing energy
  • Energy used to pump protons into intermembrane space creating electrochemical gradient
  • ATP synthase utilizes proton gradient to synthesize ATP through oxidative phosphorylation
  • Molecular oxygen serves as final electron acceptor reduced to water in complex IV (cytochrome c oxidase)

Efficiency and Regulation

  • ETC efficiency affected by uncoupling proteins and inner mitochondrial membrane permeability
  • Proton leak through uncoupling proteins generates heat instead of ATP (thermogenesis)
  • Complex I (NADH dehydrogenase) and Complex III (cytochrome bc1 complex) major sites of superoxide production
  • Inhibitors like rotenone (Complex I) and antimycin A (Complex III) disrupt electron flow and increase ROS production
  • Coenzyme Q10 supplementation may enhance ETC efficiency in certain conditions
  • Mitochondrial DNA mutations can impair ETC function leading to mitochondrial diseases

Redox Reactions in Metabolism and Signaling

Metabolic Regulation through Redox Balance

  • Redox reactions drive electron flow through metabolic pathways extracting energy from nutrients
  • NAD+/NADH ratio regulates glycolysis and citric acid cycle activity
  • NADP+/NADPH ratio influences lipid and nucleotide biosynthesis
  • Pyruvate dehydrogenase complex activity regulated by redox-sensitive phosphorylation
  • Thioredoxin system modulates activity of key metabolic enzymes through redox reactions

Redox Signaling and Cellular Processes

  • Redox-sensitive transcription factors (NF-κB, Nrf2) respond to cellular redox state changes regulating gene expression
  • Reactive oxygen species (ROS) and reactive nitrogen species (RNS) act as signaling molecules
  • Hydrogen peroxide mediates growth factor signaling through oxidation of phosphatases
  • Nitric oxide (NO) regulates vasodilation through activation of guanylate cyclase
  • Redox-mediated post-translational modifications alter protein function (disulfide bond formation, S-glutathionylation)
  • Cellular redox homeostasis crucial for proper cell function imbalances lead to oxidative stress
  • Redox reactions vital in cellular defense (production of antimicrobial compounds, xenobiotic detoxification)

Key Terms to Review (16)

Fadh2: FADH2 is a reduced coenzyme derived from riboflavin that plays a crucial role in the metabolism of carbohydrates, fatty acids, and amino acids. It acts as an electron carrier in cellular respiration, specifically in the electron transport chain, contributing to the production of ATP through oxidative phosphorylation.
NADH: NADH, or nicotinamide adenine dinucleotide (reduced form), is a crucial coenzyme in cellular metabolism that acts as an electron carrier in redox reactions. It plays a significant role in energy production by facilitating the transfer of electrons during metabolic pathways such as glycolysis and the citric acid cycle, ultimately contributing to ATP synthesis through oxidative phosphorylation.
Electron transport chain: The electron transport chain (ETC) is a series of protein complexes and other molecules located in the inner mitochondrial membrane that play a crucial role in cellular respiration. It facilitates the transfer of electrons derived from nutrients, ultimately leading to the production of ATP through oxidative phosphorylation. This process is essential for energy production in aerobic organisms and connects various metabolic pathways.
Indirect electron transfer: Indirect electron transfer is a process in which electrons are transferred between molecules through a series of intermediate steps or carriers, rather than directly between donor and acceptor molecules. This mechanism is essential in biological systems, particularly in metabolic pathways like cellular respiration, where it facilitates the transfer of energy and electrons in a controlled manner, enhancing efficiency and regulation of biochemical reactions.
Superoxide: Superoxide is a reactive oxygen species (ROS) with the molecular formula O2−, formed when molecular oxygen gains an extra electron. This highly reactive molecule plays a significant role in various biological processes, particularly in redox reactions within living systems, where it can both contribute to signaling pathways and induce oxidative stress when present in excess.
Direct electron transfer: Direct electron transfer is a process where electrons are transferred between a biological molecule, such as an enzyme or a redox-active protein, and an electron acceptor or donor without the need for any mediator. This mechanism is crucial in biological systems for energy production and cellular respiration, allowing organisms to efficiently transfer electrons during redox reactions, ultimately facilitating the conversion of energy from nutrients into usable forms like ATP.
Glutathione: Glutathione is a tripeptide composed of three amino acids: glutamine, cysteine, and glycine. It plays a crucial role in redox reactions within living systems by acting as a potent antioxidant, helping to protect cells from oxidative stress and maintaining the redox balance in biological processes. By facilitating the reduction of reactive oxygen species and other free radicals, glutathione is essential for cellular health and function.
Metabolic pathways: Metabolic pathways are a series of interconnected chemical reactions that occur within a cell to convert substrates into products, enabling the organism to extract energy and synthesize necessary biomolecules. These pathways are critical in understanding how energy is transformed and utilized in biological systems, revealing the intricate relationships between energy transfer, redox reactions, and the overall thermodynamic principles governing cellular processes.
Free energy change: Free energy change, often represented as ΔG, is the amount of energy available to do work in a thermodynamic system at constant temperature and pressure. It determines the spontaneity of a reaction: if ΔG is negative, the reaction can occur spontaneously, while a positive ΔG indicates non-spontaneity. Understanding free energy change is crucial for grasping how biological reactions are coupled and how energy is transferred and utilized in living organisms.
Oxidases: Oxidases are a class of enzymes that catalyze oxidation-reduction (redox) reactions, specifically facilitating the transfer of electrons from a substrate to molecular oxygen, resulting in the production of water or hydrogen peroxide. These enzymes play crucial roles in various biological processes, including cellular respiration and metabolism, by enabling organisms to harness energy stored in chemical bonds through redox reactions.
Photosynthesis: Photosynthesis is the process by which green plants, algae, and some bacteria convert light energy into chemical energy stored in glucose, using carbon dioxide and water as raw materials. This process is essential for life on Earth as it provides oxygen and organic compounds that serve as food for most living organisms. It also involves a series of redox reactions where water is oxidized and carbon dioxide is reduced, connecting to the principles of thermodynamics by transforming solar energy into chemical energy.
Dehydrogenases: Dehydrogenases are a class of enzymes that catalyze the removal of hydrogen from a substrate, facilitating redox reactions in which electrons are transferred. These enzymes play a crucial role in cellular metabolism, particularly in the oxidation of organic molecules and the reduction of electron carriers, contributing to energy production and various biosynthetic processes.
Reduction Potential: Reduction potential is a measure of the tendency of a chemical species to acquire electrons and be reduced. It reflects the likelihood of a substance gaining electrons in redox reactions, which are essential for energy transfer and metabolism in living systems. The higher the reduction potential, the greater the substance's affinity for electrons, influencing various biochemical processes, such as cellular respiration and photosynthesis.
Oxidation-Reduction Reaction: An oxidation-reduction reaction, commonly referred to as a redox reaction, is a chemical process in which the oxidation state of one or more substances changes due to the transfer of electrons. This type of reaction is essential in living systems as it facilitates energy production, cellular respiration, and various metabolic pathways by allowing for the conversion of energy from one form to another through the oxidation of substrates and the reduction of electron acceptors.
Signal Transduction: Signal transduction is the process by which cells convert external signals into a functional response. This involves a series of molecular events, typically initiated by the binding of signaling molecules to specific receptors on the cell surface, leading to changes in cellular activities such as metabolism, gene expression, or cell division.
Cellular respiration: Cellular respiration is a biochemical process through which cells convert glucose and oxygen into energy, carbon dioxide, and water. This process is crucial for producing adenosine triphosphate (ATP), the energy currency of the cell, and involves several key metabolic pathways that interconnect with various cellular functions, including the electron transport chain, redox reactions, and principles of thermodynamics.