Biochem ch2

Page 1: Introduction

  • Anaerobic Metabolism of Carbohydrates in the Red Blood Cell.

Page 2: Glycolysis Overview

  • Glycolysis is the central pathway for glucose metabolism in all cells.

  • Glucose is the major carbohydrate, serving as the backbone and monomer unit of cellulose and starch.

  • It is the only fuel used by all cells, including intestinal microbes, initiating glucose metabolism through glycolysis (carbohydrate splitting).

  • Glycolysis is catalyzed by soluble cytosolic enzymes.

  • The erythrocyte (red blood cell) uniquely relies on glucose and glycolysis as its sole energy source.

Page 3: Products of Glycolysis

  • Pyruvate, a three-carbon carboxylic acid, is produced as the end product of anaerobic glycolysis (2 moles of pyruvate per mole of glucose).

  • In cells with mitochondria, pyruvate converts to CO2 and H2O (aerobic glycolysis).

  • In RBCs, pyruvate is reduced to lactic acid due to the lack of mitochondria.

  • Each mole of glucose yields 2 moles of lactate, which are excreted into the blood; they contain the same number of carbons, hydrogens, and oxygens as glucose.

  • Free energy from glucose cleavage produces 2 moles of ATP per mole of glucose converted into lactate.

  • RBC uses ATP primarily to maintain electrochemical and ion gradients across the plasma membrane.

Page 4: Key Metabolites in Glycolysis

  • HO, ADP, Pi structure diagrams highlight biochemical compounds involved.

  • D-Glucose (C6H12O6) and L-Lactate (C3H6O3) structures are relevant.

Page 5: 2,3-BPG and the Pentose Phosphate Pathway

  • 10%-20% of glycolytic intermediate 1,3-bisphosphoglycerate is diverted to synthesize 2,3-bisphosphoglycerate (2,3-BPG), which regulates O2 affinity of hemoglobin.

  • The pentose phosphate pathway accounts for ~10% of glucose metabolism in RBC, protecting against oxidative stress.

Page 6: Erythrocyte Metabolism

  • RBC relies exclusively on blood glucose as a metabolic fuel and comprises 40%-45% of blood volume.

  • RBC is structurally and metabolically simple, having lost organelles during maturation, thus lacking nuclei.

Page 7: Protein Synthesis and Fuel Sources

  • Without ribosomes, RBC cannot synthesize protein or oxidize fats requiring mitochondria.

  • Dietary sugars (fructose, galactose) convert to glucose mainly in the liver.

  • RBC metabolism of glucose is wholly anaerobic due to its role in oxygen transport.

Page 8: Glycolysis Introduction

  • Overview and significance of glycolysis.

Page 9: Glycolytic Process

  • Glucose enters the RBC by facilitated diffusion via GLUT-1.

  • Glycolysis starts with glucose phosphorylation into glucose-6-phosphate (Glc-6-P), involving 10 enzymatic steps.

  • ATP is expended in investment stage to form fructose-1,6-bisphosphate (Fru-1,6-BP).

Page 10: ATP Production Yield

  • Glycolysis converts triose phosphates into lactate, producing four ATP but yielding a net gain of 2 moles of ATP per glucose, representing a low energy extraction efficiency compared to mitochondrial processes.

Page 11: Interconnected Pathways

  • Glycolysis has 10 steps to convert glucose to lactate, allowing glycolytic intermediates to link into other metabolic pathways (fats, proteins, nucleic acids).

Page 12: Metabolic Branch Points

  • Intermediates linking glycolysis with other pathways (glycogen, sugars, ribose for nucleotides).

Page 13: Glucose-6-phosphate Entry

  • GLUT-1 transporter facilitates glucose uptake.

  • Phosphorylation of glucose to Glc-6-P by hexokinase is the commitment step, trapping glucose inside RBC.

Page 14: Conversion to Fru-6-P

  • Conversion of Glc-6-P to fructose-6-phosphate by phosphoglucose isomerase.

  • Further phosphorylation of Fru-6-P by phosphofructokinase-1 (PFK-1) investing another ATP.

Page 15: Glycolytic Enzyme Reaction Summary

  • Detailed representation of enzymatic reactions involving hexokinase, phosphoglucose isomerase, and PFK-1.

Page 16: Commitment to Glycolysis

  • Fru-1,6-BP is a crucial intermediate regulating entry into glycolysis, catalyzed by PFK-1 with irreversible action.

Page 17: Aldolase Reaction

  • Aldolase yields two triose phosphates from Fru-1,6-BP, continuing glycolysis.

  • Glyceraldehyde-3-phosphate proceeds through the yield stage while dihydroxyacetone phosphate interconverts for complete metabolism.

Page 18: Yield Stage Details

  • The yield stage of glycolysis produces 4 ATP per 2 triose phosphates and nets 2 ATP per glucose.

Page 19: Substrate-Level Phosphorylation

  • High-energy phosphate transfer from acyl phosphate compound (1,3-BPG) to ADP to form ATP in substrate-level phosphorylation.

Page 20: GAPDH and ATP Generation

  • The oxidizing reaction of glyceraldehyde-3-phosphate catalyzed by GAPDH traps phosphate, regenerating NAD+ and forming high-energy 1,3-BPG.

Page 21: Substrate-Level Phosphorylation Reaction Overview

  • Enzymatic steps that convert 1,3-BPG to ATP.

Page 22: Further Phosphorylation Steps

  • The conversion of 2-phosphoglycerate to phosphoenolpyruvate (PEP) involves dehydration reactions leading to ATP production.

Page 23: ATP Generation Mechanism

  • Substrate-level phosphorylation yields ATP via glycolytic enzymes including PGK and PK.

Page 24: Pyruvate Formation

  • The process involved in forming pyruvate and generating the second ATP via substrate-level phosphorylation.

Page 25: Glycolytic ATP Summary

  • Total ATP production analysis reveals a net yield of 2 moles of ATP.

Page 26: Regeneration of NAD+

  • LDH regenerates NAD+ by converting pyruvate to lactate, allowing continued anaerobic glycolysis.

Page 27: Anaerobic vs Aerobic Conditions

  • LDH activity under anaerobic conditions yields lactate while aerobic conditions lead to CO2 and H2O by mitochondria, with lactate forming under hypoxic conditions.

Page 28: Fermentation Processes

  • Fermentation, the anaerobic metabolism term, varies among organisms: bacteria, yeast converting pyruvate to lactate or ethanol.

Page 29: Yeast Fermentation Steps

  • Decarboxylation of pyruvate followed by ethanol production in yeast.

Page 30: Nutritional Aspects of Fermentation

  • Alcohol yields energy between carbohydrates and lipids and contributes to numerous fermented food products.

Page 31: Gut Microbiota and Fermentation

  • Role of anaerobic bacteria in digestion and immune protection, influenced by dietary composition.

Page 32: Glycolytic Regulation

  • Overview of regulation mechanisms in glycolysis.

Page 33: Allosteric Regulation in RBCs

  • Glycolysis is regulated at three critical enzyme steps, aligning with the energy requirements of the RBC.

Page 34: Hexokinase Regulation Mechanism

  • Hexokinase activity Feedback inhibition by its product, glucose-6-phosphate (Glc-6-P).

Page 35: Primary Regulation by PFK-1

  • PFK-1 is the main regulatory step influenced by ATP and AMP concentrations in glycolysis.

Page 36: ATP's Dual Role

  • ATP acts as both a substrate and an allosteric inhibitor of PFK-1, allowing tight regulation.

Page 37: AMP Activation

  • The concentration difference between ATP and AMP regulates PFK-1 activity, enhancing glycolysis during higher energy demand.

Page 38: Energy Status Sensitivity

  • PFK-1 activity correlates with the (AMP + ADP)/ATP ratio, modulating glycolytic rate.

Page 39: Glycolytic Regulation Feedback Loop

  • Feedback mechanisms adapt glycolytic rates during varying energy states.

Page 40: Pyruvate Kinase Activation

  • Pyruvate kinase is allosterically activated by Fru-1,6-BP, preventing triose phosphate accumulation.

Page 41: Characteristics of Regulatory Enzymes

  • Features of regulatory enzymes: responsiveness, low Vmax, and catalyzing irreversible reactions.

Page 42: Complex Regulation in Other Tissues

  • Glycolysis regulation is more intricate in tissues other than RBC due to variable fuel consumption and metabolic flexibility.

Page 43: Regulation Summary Table

  • Summary of glycolytic enzyme regulation in the red cell, detailing inhibition and activation mechanisms.

Page 44: Pentose Phosphate Pathway Overview

  • Overview of the pathway designed for nucleotide synthesis and interaction with glycolysis.

Page 45: Shunting and Recycling in the Pathway

  • The pentose phosphate pathway acts as a shunt, converting pentoses back to glycolytic intermediates as needed.

Page 46: NADPH Generation in the Pathway

  • NADPH's primary role in lipid biosynthesis and detoxification highlighted, especially in the liver and RBC.

Page 47: Mechanisms of NADPH Production

  • NADPH produced through specific enzymatic reactions in pentose phosphate pathway.

Page 48: Enzyme Usage Difference

  • Distinction between NAD(H) use in glycolytic enzymes and NADP(H) in pentose phosphate pathway.

Page 49: NADPH Production Reaction Diagram

  • Visual representation of NADPH-producing reactions in the pentose phosphate pathway.

Page 50: Interconversion of Five-Carbon Sugars

  • Conversion processes of ribulose-5-phosphate back into glycolytic intermediates for nucleic acid synthesis in active cells.

Page 51: Summary of Equilibrium Reactions

  • Enumeration of equilibrium reactions that recycle pentose phosphates into glycolytic intermediates.

Page 52: Equilibrium Reaction Table

  • Table summarizing substrates and products of equilibrium reactions within the pentose phosphate pathway.

Page 53: Glucose Shunting in RBC

  • Emphasizes temporary diversion of glucose in pentose phosphate pathway with focus on continued glycolytic activity.

Page 54: GSH and Oxidative Protection

  • Glutathione's role as an antioxidant, necessitating NADPH for its reduced form maintenance.

Page 55: GSH Chemical Structure

  • Structure and relevance of GSH in cellular function and protection mechanisms.

Page 56: Glutathione Reactions

  • Role of glutathione reductase and peroxidase in detoxification processes, with visual representation.

Page 57: Glutathione Functions Overview

  • Protective roles of GSH in the cell's oxidative defense extending to protein stabilization.

Page 58: GSH Protein Interaction

  • GSH's function in maintaining protein thiol groups in reduced states, preventing oxidative crosslinking.

Page 59: References

  • Links to additional video resources relating to the anaerobic metabolism of carbohydrates in red blood cells.