CAMPBELL & REECE CHAPTER 9 metabolic pathways that released stored nrg by breaking down complex molecules a catabolic pathway partial degradation of sugars or other organic fuel anaerobic not as efficient as aerobic respiration generally means aerobic cells mostly use glucose as fuel energy released: ATP + heat (so is exergonic) nrg released: ΔG = -686 kcal/mol [2870kJ] answer based on transfer of e- during chemical reactions moving e- releases nrg stored in organic molecules which is ultimately used to synthesize ATP substance giving away e- is called the reducing agent substance taking e- is called the oxidizing agent some do not involve complete transfer of e- (as in forming ions) *generally, organic molecules that have lots of hydrogen make excellent fuels because their bonds are source of “hilltop” e- whose nrg will be released as the e- “fall” down nrg gradient when transferred to O2 H is transferred from glucose O2 as e- transferred nrg state of e- is lowered that released nrg is available for ATP synthesis without EA barrier, glucose or other foods would spontaneously combine with O2 in air body temperature not high enough to initiate combustion of glucose, enzymes required to lower EA glucose & other molecules are broken down in series of steps (each w/own enzyme) @ key steps e- are stripped from glucose each oxidation step involves e- traveling with H atom NAD+ NADH oxidized state reduced state Nicotinamide Adenine Dinucleotide derivative of niacin enzymes called dehydrogenases remove a pair of H atoms (with 2 e-) from substrate (glucose) thereby oxidizing it. dehydrogenase then delivers the 2 ealong with 1 H (1 proton) to its coenzyme NAD+ 2nd H+ is released to surroundings by receiving 2 e- & 1 H+, NAD+ loses its (+) charge NAD+ most versatile e- acceptor in cellular respiration (used in several redox reactions) When e- passed from glucose NAD+ they lose very little of their nrg cellular respiration uses e- transport chain to break fall of e- O2 into several nrg-releasing steps consists of a # of molecules (proteins mostly) in inner membrane of mitochondria & plasma membrane of those prokaryotes that have aerobic respiration @ “top” of chain NADH carries higher nrg e- removed from glucose “bottom” of chain lower nrg e- passed to O2 e- transfer from NADH O2 is exergonic reaction with a free energy change of : -53 kcal/mol (-222 kJ/mol) instead of releasing all that nrg in 1 explosive step, e- cascade down the chain from 1 carrier molecule to next in series of redox reactions each carrier is more electronegative than previous molecule O2 is final e- acceptor because it is the most electronegative can think of it as O2 pulling e- down the chain in nrg-yielding tumble 1. 2. 3. Glycolysis Pyruvate Oxidation & Citric Acid Cycle Oxidative Phosphorylation e- transport chain chemiosmosis 1. 2. 2 parts: Energy Investment Phase Energy Payoff Phase anaerobic in cytoplasm no CO2 released uses 2 ATP, makes 4 ATP 2 NAD+ + 4 e- + 4H+ 2 NADH + 2H+ glucose 2 pyruvate + 2 H2 O pyruvate mitochondria via active transport (eukaryotic cells) pyruvate stays in cytoplasm in prokaryotes that perform aerobic respiration 1. 2. 3. Pyruvate’s carboxyl group (already oxidized so has little chemical nrg) is removed as CO2 Remaining 2 C fragment is oxidized acetate (ionized form of acetic acid) with e- NAD+ NADH CoA (derived from vit. B) attached via S atom to acetic acid acetyl CoA aka: Krebs Cycle tricarboxylic acid cycle functions as metabolic furnace that oxidizes organic fuel derived from pyruvate for each acetyl group entering cycle: 3 NAD+ 3NADH 1 FAD + 2 e- + 2H+ 1 FADH2 * 1 GDP + 1ATP 1GTP + 1ADP * GTP made in many animal cell mitochondria: GTP similar to ATP in structure & function /example of substrate-level phosphorylation @ end of Citric Acid Cycle only have 4 ATP made (counting glycolysis) also have NADH & FADH2 (hi nrg ecarriers) which accounts for most of nrg extracted form glucose collection of molecules embedded in inner membrane of mitochondria (prokaryotes have them embedded in their plasma membrane) inner membrane has multiple folds allowing for multiple copies of etransport chain to be working at same time most of the molecules are proteins, rest are nonprotein components necessary for catalytic functions of certain enzymes there is a drop in free nrg as e- move thru e- transport chain alternating reduced state oxidized state http://www.johnkyrk.com/mitochondrion. html http://highered.mcgrawhill.com/sites/0072507470/student_view0 /chapter25/animation__electron_transport_ system_and_formation_of_atp__quiz_1_.html http://www.science.smith.edu/department s/Biology/Bio231/etc.html http://www.dnatube.com/video/2354/Det ailed-ElectronTransport-Chain http://vcell.ndsu.nodak.edu/animations/et c/movie-flash.htm e- transport chain makes no ATP directly it does break the fall of e- from food to O2 into a series of smaller steps that releases nrg in manageable amts for every 4 e- 1 O2 + 4 H+ 2 H2 O (O2 is final e- acceptor) inner membrane protein ATP Synthase makes ADP + Pi ATP using the proton (H+) gradient as nrg source chemiosmosis is the process in which nrg stored in H+ gradient across membrane is used to drive cellular work (see animations) % of chemical nrg in glucose ATP oxidation of 1 mol glucose under standard conditions = 686 kcal/mol 1 ATP stores 7.3 kcal/mol efficiency of cellular respiration = 7.3kcal/mol x 32mol ATP/1 mol glucose÷ 686 kcal/mol = 0.34 34% actually a little higher: under cell conditions ΔG is lower 66% of nrg from oxidation of glucose lost as heat adaptation in hibernating animals: use brown fat: cells packed full of mitochondria & that has a protein in inner membrane that allows H+ to flow down its concentration gradient w/out making ATP (so oxidation of stored fats generates heat w/out making ATP) Brown Fat w/out this adaptation ATP would build up to point where cellular respiration would shut down 1. 2. without an adequate supply of O2 “pulling” e- thru transport chain oxidative phosphorylation eventually stops 2 things cells can do to get some ATP out of organic fuel w/out O2 Anaerobic respiration Fermentation uses e- transport chain (fermentation does not) used in anaerobic bacteria: have e- transport chain but O2 is not the final e- acceptor some marine prokaryotes use (SO4 -²) sulfate ion as final e- acceptor H2 S uses no O2 & no e- transport chain is extension of glycolysis in cytoplasm that generates ATP by substrate-level phosphorylation of glycolysis & recycles NADH back to NAD+ 1. 2. Alcohol pyruvate ethanol in 2 steps: 2 pyruvate 2 CO2 + 2 acetaldehyde 2 acetaldehyde + 2 NADH 2 ethanol + 2 NAD+ Lactic Acid pyruvate is reduced directly by NADH lactate (end product) lactate is ionized form of lactic acid used by fungi & bacteria to make cheese & yogurt 1. 2. 3. all 3: produce ATP by harvesting chemical nrg in food use glycolysis to oxidize glucose pyruvate with a net production of 2 ATP by substrate-level phosphorylation use NAD+ as oxidizing agent methods of oxidizinf NADH NAD+ 1. Fermentation pyruvate or acetaldehyde 2. Anaerobic Respiration e- transport chain atom less electronegative than O like S H2S 3. Aerobic Respiration e- transport chain O2 H2O oxidative phosphorylation yields up to 16x more ATP/glucose molecule only carry out fermentation or anaerobic respiration O2 is toxic to them yeasts & many bacteria make enough ATP to survive w/out aerobic oxidation but if O2 available can go thru oxidative phosphorylation muscle fibers (cells) can behave as faculative anaerobes ancient prokaryotes used glycolysis to make ATP b/4 O2 present in atmosphere oldest prokaryotes: 3.5 billion yrs old 2.7 billion years ago O2 in atmosphere: source: cyanobacteria thru photosynthesis Glycolysis is a metabolic “heirloom” from early cells that continues to function in fermentation & as 1st stage in breakdown of organic molecules by respiration Glycolysis & Citric Acid Cycle lead to many other metabolic pathways food we eat has very little glucose in it: glycolysis can accept other carbohydrates glycogen breaks down to glucose disaccharides monosaccharides 1st broken down to their a.a. those not needed for protein synthesis can be converted to intermediates of glycolysis & Citric Acid Cycle 1st amino group removed (deamination) 1st glycerol & fatty acids glycerol glyceraldehyde 3-phosphate (intermediate in glycolysis) fatty acids beta oxidation 2-C fragments Citric Acid Cycle as acetylCoA beta oxidation process generate NADH & FADH2 e- transport chain (reason why lipids have more nrg stored than carbs) cpds formed as intermediaries in glycolysis & Citric Acid Cycle diverted to anabolic pathways as precursors cell uses to synthesize what it needs (using ATP in process) a.a. (can make ~12) pyruvate glucose acetyl CoA fatty acids cells use supply & demand principles (does not synthesize more cpds than it needs) Feedback inhibition: end product of anabolic pathway inhibits enzyme(s) that catalyze early step of pathway if cell “working” harder will speed up rate of respiration when plenty of ATP for work cell is doing production slows down control achieved by regulating enzymes @ strategic places in pathway enzyme in glycolysis that catalyzes addition of 2nd phosphate group which is 1st step that commits the substrate irreversibly to glycolytic pathway allosteric enzyme: has receptor sites for specific inhibitors & activators inhibitor is ATP activator: AMP is also sensitive to concentration of citrate: when citrate builds up in mitochondria some diffuses into cytoplasm and acts as inhibitor The energy that keeps us alive is released, not produced, by cellular respiration