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NH2 Biologically relevant form : Add Mg2+ O O O -...

NH2 Biologically relevant form : Add Mg2+ O O O - N N 1 no-P-0-5-0-P- O O N N- I ( I - ! + -.. o ON H Mgz [products) ATP ADD + Pi DG DG' + RT In [reactants] - = reactant product [ADP] [Pi] - G = DG' + RT In [ATP] DG = - 30 5. 47/mo 30500 /mol - = = 3 3 4 8 - R 8 314 - 1 32 x 10 x x 10 molk m =... 298 K In M. · 3 D6 -30500 + 8 314 K 3. 38 10 - =.. x o (273 + 25)K 3) ° 298K 3 (1 T = 25 C = = 32 x 4 3 x 10- (8.. in K F always - - 30500 +. 314 x 298 x In 3. 38 mol 3 [ADP] - = 1. 32 MM = 1 32 x. 10 M F = 4 8 MM 3 M (2 In 001875) - [Pi] =. = 4 8. x 10 = - 30500 -. 314 x 298 x 0. mol mol 3 [ATP] = 3 38. MM = 3 38. x 10- M 305005 (8 28) - = - + 314 < 298 X ( 6 - = - 30500 - 15559 = - 46 059 d...  3 10 - 3 - [ADP] [Pi] 1 32 x x 4 8 x 10 =.. -305005, * G = DG' + RT In [ATPY De = + 8 314. mol. K * 310K n. 38 3 x 10 - 3 ↳ only changes F - = 30500 + (8 314 x310x ( 6 -. 28) 0 = - 46684 => Reaction becomes er mol. ° T 37 C (37 273)K 310 K exergonic = + more = = ↑ - Energy charge indicator of the energy level in cell = Why important ? ↑ EC - PATP => ANABOLISM (produce other molecules) DEC- ATP = CATABOLISM (produce ATP) Normally between 0 8-0 95.. In case of severe ATP deficiency => use ADP to form ATP signal for critically low EC - LADP = ATP + AMP Transphosphorylation of nucleotides At any given point => in time , one can use half of the ADP reserves to ATP produce creason why ADP contributes to Ed  [ATP] + 2 [ADP] 3 38MM + 2 x 1 32 MM. 4 04 mi. 81. = I = 0. ECE [ATP] + [ADP3 + [AMP] 3 38 MM. + 1 32 MM +. 0 29 MM. 4 99 MM. [C] x[D] Reaction Quotient = [A] x [B] - can be defined at any point of the rxn -shows the relationship between the concentrations of reactants and products [CJeg x [D]eq Equilibrium constant = [Ajeq * [B] eq Equilibrium : rate of forward rxn-rate of reverserxn => concentrations of reactants and products remain constant = Keq is only defined for equilibrium cord. A +B < "C + D and shows the relationship between conc. of reactants and products at equilibrium. Rate of Rate of => no work > DG = 0 forward - = reverse rxM rxM Under equilibrium conditions : DC' DG' 0 = + RTInKeg = = - RTInkeg DG'O RT => Keg = e ~ DG'O 30500 mo RT 8 3147x298k. 31 12 Keq C. = = = e molk C = 221903 = 2 2x. 105 Under normal conditions , the concentrations of reactants and products in the cell are far from equilibrium. 1 32. x 10-3 x 4 8. x 10-3 1 87 3 Q - = 3. 38x10-3 =. x 10 1x108 Keq = T = 298 K DG° = - RT In Kea = R 8 314 F In 108 = 298Kx. molk = - 8 314. x molxk = F - 45 638. mol  likes to donate e likes to gain e => The more positive the value , the more it likes to gain e => e-will always flow from more negative to more positive El ~ donor ~ acceptor 2) NAD+ /NADH because of lower DE (gains et b) oxidizing agent = compound that gets reduced Pyruvate (gets reduced to lactate) : higher DE' value = accepts e  NADT + H+ + 20- > NADH DE = -0. 320 V -flow 2H + + lactate DE 190V Pyruvate + 20- -0. = > DE 130V (ALWAYS POSITIVE) Eacceptor-Edonor 190V = = -0. + 0. 320V = 0. Acceptor-Donor (A) : Pyruvate + 2H++ 20- > lactate + 20 NAD H+ + NADH - (D) : + > -t Pyruvate + 2H + + 20- + NADH +. flow from donor to (from (a)) will proceed towards e-always acceptor rxn lactate formation ° + = 25 C , IM = Standard cord GO pHE C =. > D = , DG' = - N. F. DEO = - 2 x 96. 545 x 0. 130V W. Mol = - 25. 1 47/mdl exergonic ran (Another confirmation for d) E - DG'O 25/00 mol Keq = e RT - e 8 312. Emol * 298K = , 10. 13 = 2 51. x 104  Catabolism Anabolism > complex structures into building blocks - simple compounds produce more complex ones oxidize compounds (reduced > oxidized reduce compounds (oxidized - reduced) > - - ATP > production ; reduced e-carriers consume energy CNADH ; FADH2) is released is stored energy that > LOW EC (cell needs to produce ATP) High EC (cell has a lot of Atp/energy)  &= Oxidation state of H2 O H2 is more reduced than He can act as e-donor : CO2 = Chas more et Oxidation state of carbon in CD2 : + 4 In order to use it as a building block the Cin C02 needs to be reduced use e-from He for CO2 assimilation (reduction & incorporation into molecules) organic => CHEMO LITO AUTOTROPHY - ↑ - get co2 from ↓ use in organic atmosphere energy from compounds chemical rxn Credox) O L A) Acyl-CoA - S-COA 0- ↳ Thioester bord stabilization ( e C , ( by - : no resonance "O - o- t high energy bord - releases when cleared energy O 11 B) Glucose 46 bisphosphate D) Q-OH E C OH O i OH S S i - O -P 3) Phosphoend pyruvate H - C Trapped in end form i - O-P H-OH Lipoic acid = cofactor Cheto is more stable) CH2 No keto-end tautomerism. => release of a enables heto-end tautomerism  0 + -H c i H 9 - H - CH2OH [PFK 1) CH2O P c = 0 Phosphohexose d I CH2O Got HotDo nexolie ene isomerase phosphofructo T C 0 = 0 P Aldolase = Kinase I > C > HO - C - H D HO-C-H S dihydroxyacetone P (DHAP) ATP ADP H-C-OH ATP DP I N H-C-OH - Triose Phosphate Isomerase (TIM) ~ H -q-OH H - 1 - OH H-'c-OH CH2OH H-G-OH CH2O P CH20 P CH2O I P H - I C-OH CHLOH I CH2O P glucose glucose 6P fructose GP fructose 1, 6 bis p glyceraldehyde 3 P (GAP) NADH GAP dehydrogenase Pi - - NADH + H+ V Q-0- · -0- Oc -0 - P -o 3PGA Kinase " Oc O Pyruvate Kinase C Enolase PGA mutase C-OH < > H - -OH - % 2 - H CH20 - c L 0 P < > H - 0 P ADP "TP P Fizo - - CH20 - - = 0 ADP "ATP "Hz CH2OH P CH3 1, 3 bis phosphoglycerate phosphoend pyruvate 2 phosphoglycerate 3 phosphoglycerate pyruvate d) coupling reactions drive very endergonic by coupling it with : a reaction a very exergonic reaction GAPDH reaction CH2O P CH2O I P H-C-OH H-C-OH NADH NADH NADH NADT H'I "O > CH2O I P > CH2O P P of do ↑ , H-C-OH H- C-OH - > do I Pindo I - SQ S S I I I cis Cys Cys CyS Formation of thioester bord. (store energy) of coupling rxn : (1) Exergonia : 0 - H 90 I Aldehyde Oxidation H-C-OH + NADT > H-C-OH + NADH+ HA H I (DG = - 50 47/mol) CH20 P CH20 P Q "C -or - 0 - P - (2) Endergonic O I C Anhydride bond H- --OH t - O-P-OH 7 H-C-OH t H2O [DG = 56 47/MOD I CH2O P - CH2O P 3) 1 Hexohinase traps glucose inside of the cell. : glc > glc64 :. 2 Phosphofructokinase : Fru 6P fru6bisp : determines progression into glycolysis. 3 Pyruvate hinase PEP how are they regulated 2. EC , ATP > draw ATP ~ definition of EC -high energy compounds draw. 3 Glycolysis namet enzymes a know" special reactions : e.. g GAPDH) pyruvate hinase - Carriers : NADT ; FAD  PDH reaction mechanism (1) El : PYRUVATE DECARBOXYLATION % -o vo R S C ha gro Di & CH3 · TPP pyruvate Hydroxyethyl-TPP (2) E2 : THINESTER FORMATION O S-COA Res -( - To t oxc-S-co R- S ° + H+ HS C S I > - 7 t H S Is Ri Lys i It Lys Lys Acetyl-CoA lipoic acid Lys Hydroxyethyl-TPP Lipoate Creduced) coxidized) (3) Ez : e TRANSFER D NADH -S , HS + FAD ↑ > FAD HS Lys Lys Prosthetic groups : TPP , lipoid acid , FAD ↳ associated with the do not diffuse enzyme , away, have different DE depending on enzyme Co-substrates : COA , NAD + ↳ diffuse after reaction is away completed , same Del TPP > - Vitamin B1 ↑ FAD > - Vitamin B2 Lipoic acid is not derived + NAD > - Vitamin B3 from a vitamin precursor , COA- > Vitamin B5  NADT > Nicotinamide Adenine Dinucleotide COA FAD > Flavin Ademine Dinucleotide THINESTERS 1. High energy compounds - it-electrons trap Donor of 2. acyl groups > thioester bond is labile < Excretion Crole of lactate is to refill the pool of NADT) 9 P OH OH x) - POH - C ↑ transfer O -OH Carbonyl containing group - ( ?) C C po HN HN H - H - + need to use TPP - - - => it J Do I CH3 CH2 CH2 Alanine c oh O"OH pyruvate X-heto glutarate glutamate Transamination run  far from the "force" that drives the metabolism 1. In our bodies , overall DG is far from O = reactions are kept equilibrium , this being. 2 when a reaction is at equilibrium (DG = 047/mol) no work is produced want the substrate to be for them to be at 3. Normally you continuously turned into product , not equilibrium. => In order to metabolism for this organism rid of keep running > need to get products. just excreting the product might not be. enough - Ce. g.. there might be a way for it to get back into the cell/ it might be toxic => Need interaction with another organism that takes up the product & metabolizes it. (SYNTROPHY) form (stick to other How do you see this in nature ? Over generations the organisms consortiy each  o c Yo Po [ LDH HC I -