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10/12/11 enzymes are catalysts - allow reactions to occur faster in biological systems enzyme is a type of protein substrate binds

nds to enzyme enzyme-substrate complex formed reaction occurs and product is formed catalysts lower activation energy - less energy needs to be put in to allow reaction to occur

catalysts do not affect net change in free energy (G) - G for catalysed and uncatalysed reactions are the same enzymes position reactants so that they can react to form specific products enzymes used to synthesise/break down substances enzymes can add/remove charges (+) and (-) oxidation - loss of electrons (oxidised molecule loses the energy contained by electrons) reduction - gain of electrons (reduced molecules gain energy contained by electrons) enzyme conformation changes when substrate binds cofactors, coenzymes, prosthetic groups help enzymes function cofactors - metal ions coenzymes - many vitamins act as coenzymes, loosely bound to enzyme prosthetic groups - covalently bonded to enzyme (permanently integrated into enzyme) reaction rate sped up by presence of enzymes reaction rate sped up by higher substrate levels to a limit - limited by amount of enzyme available, natural systems have a limited amount of enzyme enzyme reactions do not occur in isolation - different metabolic systems present within living systems all living systems metabolism is catalysed by enzymes reactions is biological systems controlled by amount of enzyme, inhibition - genes control enzyme production, enzyme can be directly modified irreversible inhibition - a molecule binds to the active site and blocks the substrate, renders enzyme permanently unusable eg. DIPF inhibits trypsin enzyme, carbon monoxide poisoning competitive inhibition - competitive inhibitor binds to active site and blocks substrate, reversible noncompetitive inhibition - noncompetitive inhibitor binds to allosteric site and changes shape of enzyme and active site to block substrate allosteric site - non-active site area of enzyme

10/14/11

to overcome competitive inhibitor, increase concentration of substrate some enzymes are regulated by binding of inhibitor/activator molecules to allosteric site inactive without allosteric activator bound to enzyme feedback inhibition - the end product of a pathway is used as allosteric inhibitor for an enzyme in the pathway

optimal pH - enzymes operate most efficiently at certain pH levels eg. pepsin (in stomach) has very acidic optimal pH optimal temperature - reaction rate increases as temperature increases until optimal temperature is reached, any temperature above optimal causes protein to begin denaturation temperature vs reaction rate graph is left-skewed distribution Chapter 9 - Cellular Pathways that Harness Chemical Energy glucose metabolised so cells can trap free energy in the form of ATP sun photosynthesis glucose glycolysis pyruvate cellular respiration (aerobic respiration) or fermentation (anaerobic respiration) aerobic (requiring oxygen) respiration is more efficient in trapping energy for use larger, higher order organisms (eg. humans) use this process

anaerobic (no requiring oxygen) respiration produces less ATP to use for work smaller, simpler organisms tend to use this process oxidation and reduction are coupled - redox reactions NAD+ is an oxidising agent (gains and carries electrons), NADH is a reducing agent (loses and passes on electrons) - cyclic process 10/17/11 reduction: NAD+ + 2 H NADH + H+ oxidation: NADH + H+ NAD+ + 2 H respiration in eukaryotes - glycolysis and fermentation occur in cytoplasm, citric acid cycle and pyruvate oxidation in mitochondrial matrix respiration in prokaryotes - glycolysis, fermentation, citric acid cycle occur in cytoplasm, pyruvate oxidation and respiratory chain associated with inner face of plasma membrane glycolysis and cellular respiration: glycolysis (glucose pyruvate) pyruvate oxidation citric acid cycle respiratory chain glycolysis and fermentation: glycolysis (glucose pyruvate) fermentation lactate or alcohol facultative anaerobes (eg. yeast) can use fermentation and cellular respiration overall cellular respiration reaction: C6H12O6(glucose) + 6 O2 6 CO2 + 6 H2O

energy-investing reactions in cellular respiration: Glycolysis enzymes and energy from 2 ATP used to break down glucose into G3P (glyceraldehyde 3-phosphate aka PGAL) G3P oxidised by NAD+ (NADH produced carries electrons to electron transport chain) to form BPG, BPG used to from 2 ATP and PGA (3-Phosphoglycerate aka PGA) PGA converted to PEP and 2 water molecules produced 2 ATP produced in conversion of PEP to pyruvate note: kinase enzyme produces ATP outside of mitochondria - substrate-level phosphorylation Pyruvate oxidation pyruvate oxidised by NAD+ to form Acetyl CoA (acetyl-conenzyme A) Citric acid cycle acetyl CoA used in citric acid cycle to produce NADH and FADH2 (electron carriers), H+, CO2 and 2 ATP - cycle occurs twice to oxidise 1 glucose 10/19/11

NADH formed by hydride ion reduction coenzyme A detached from molecules when it has served its purpose GTP is produced and converted to ATP for use Electron transport chain proteins embedded in inner mitochondrial membrane accept electrons carried by NADH and FADH2 (which become NAD+, FAD) and pass them along to a terminal electron acceptor oxygen is terminal electron acceptor - O2 reduced by electron transport chain (ETC) to form water, ETC cannot function without oxygen oxygen can accept electrons from ETC because of cytochrome c oxidase protons stripped from NADH and FADH2 - protons (H+) pumped out of matrix into intermembrane space, H2O produced within matrix ATP synthesised via chemiosmosis - higher concentration of H+ in intermembrane space (due to ETC proton pumps) causes H+ to diffuse across inner mitochondrial membrane H+ diffuses through ATP synthase embedded in inner membrane, chemiosmosis powers ATP production

experiment in textbook showed that proton (H+) gradient drives ATP synthesis another experiment showed that ATP synthase is necessary for ATP synthesis Anaerobic respiration (fermentation) glycolysis occurs to for 2 pyruvate molecules from 1 glucose molecule fermentation produces lactic acid or ethanol (alcohol) constant supply of NAD+ needed to sustain fermentation CO2 produced in alcohol fermentation Aerobic vs Anaerobic efficiency - 32 ATP produced in cellular respiration, 2 ATP produced in fermentation

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