Catalytic Strategies

Serine Proteases

Catalytic Triad

Serine, Histidine, Aspartate

S1 Pocket

Oxyanion Hole

Mechanism

Steps

Inhibition

Serpins / alpha-1-antitrypsin & elastase

Other Proteases

Cysteine proteases, metalloproteases, aspartyl proteases

Carbonic anhydrase

Restriction/ Modification Systems

Allostery & Regulation

Allosterism

ATCase & effectors

Covalent Modification

Zymogens

Proteases

Phosphorylation, acetylation, formylation, acylation, ADP ribosylation,

prenylation, sulfation, ubiquitination, carboxylation

Blood Clotting

Cascading amplification

Cellular Response

Platelets, calcium, von Willebrand factor, thromboxane

Molecular Response

Intrinsic pathway / Extrinsic pathway

Convergence on Factor X

Activation of thrombin in first phase

Amplification phase increases thrombin 1,000,000 fold

Thrombin converts fibrinogen to fibrin

Soft clot / transglutaminase

Carboxylation / vitamin K / Warfari / Ca++

Plasmin / tPA

Carbohydrate Structure

Hexoses / pentoses / tetroses / heptoses / octoses

Monosaccharides

Glucsoe, ribose, galactose, fructose

Aldoses / ketoses

Stereoisomers / enantiomers / epimers / diastereomers / anomers

Cyclization

Fischer vs Haworth

Furanose / Pyranose

Glycosides

Artificial sweeteners

Disaccharides

Sucrose, lactose, maltose

Oligosaccharides

Glycoproteins

Identity

Polysaccharides

Cellulose, glycogen, amylopectin, amylose, chitin

Glycosaminoglycans

N-acetylgalactosamine / N-acetylglucosamine based

Heparin, hyaluronic acid, chondroitin sulfate

Proteoglycans / peptidoglycan

Hyaluronan

Lectins / phytohemagglutinins

Flu / tamiflu

Glycolipids

G-Protein Coupled Receptors

Activation by Hormone Signaling

Epinephrine

Glucagon

Inactivation

Arrestin system

GTPase of alpha subunit

Phosphodiesterase action on cAMP

Inhibits PKA

Inhibited by caffeine

Coffee ‘buzz’

Receptor Tyrosine Kinase (RTKs)

Phosphorylation

Dimerization caused by ligand

Membrane Bound

Autophosphorylation

Signaling Complex

RTK Examples

Insulin Receptor

Always a dimer

IRS-1 & other signaling

Stimulate GLUT 4 movement & glucose uptake

Activates Phosphoprotein phosphatase

Opposes of B-adrenergic pathway

Epidermal Growth Factor (EGF) Receptor

Dimerizes on binding EGF

Stimulates growth, proliferation, differentiation

Ras

Similar to alpha subunit of G-protein

GTPase

Stimulates replication

Effects of mutation

Steroid Hormone Signaling

Effects

Metabolism, Inflammation, Immune system, salt balance, sex

characteristics

Steps in action

Release in blood, crossing lipid bilayer, binding receptor, effects on

transcription

Other Signaling

Nerve transmission

Prostanoids

Signaling Gone Wild

Oncogenes, Proto-oncogenes & Mutations

RAS

GTPase function and effects

Src and control of cell division

HER2

Herceptin

BCR-ABL translocation

Gleevec

Metabolic Energy

Catabolism

Makes ATP, NADH

Anabolism

Uses ATP, NADH

Gibbs Free Energy

∆G = ∆G°’ + RTln({Products}/{Reactants})

Values ∆G and Reaction Direction

∆G°’ and Creatine Kinase

ATP and Potential Energy

Oxidation / Reduction

Energy Coupling

Metabolic Pathways

Roadmaps

Interconnectedness

Central Metabolic Pathways

Glycolysis

Oxygen / Fermentation

Citric Acid Cycle

High Energy Intermediates and Energy Barriers

Glycolysis