Lecture21-Ch13-1-Oct29_2007

Lecture21-Ch13-1-Oct29_2007 - Photosynthetic autotruphs...

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Unformatted text preview: Photosynthetic autotruphs Energy- ntairling nutrient: Carbohydrate-a Fats Proteins _ Gall Precursor macromolecules muleeulea Pruteins 1 Amino acids Pnlyaaccharidea ' Sugars lipids I Fatty acids Nucleic acids E Nitmgennus bases B'me Carat-amid Etemid ' pigments hnrnmuE-a I I Fhusphulipida Tsnmnte111r‘l- lec \ pimphufiphum‘ Chulesner-nl Hulda Tl'iaqlrlglarcemla * Fatty adds I x Mevalnnane Vitamin K Ulmlestfi'ryl I L'El-Erfi ‘ Mmumwl-Gflfi Emmett; \ Starch Alanan Fhemrl ' H H alanine Ely-cage]; fir Gluma-e *P‘gnuvate fl fl“ SLLE’I'UEE! Sarina Luuuiru: Iauleucine Fatty “d5 TTiHENlE'l'PEEIUlE Eunverflin: mtahuliam A x ml Citrate CDP—diacylgflmern] ‘- thphnlipida finluamtate ‘ Dimming ambuljam [III-II I“ ma; Hm: Cyclic pathway {-3) DO—fi—°—'i'—0 m 0' 0' ATP4' O -0_F|1_0H (D hydrolysis, I with relief 0— ofcharge resonance rePUISion ® stabilization 5' 3— D. _ ."'|‘\.._ _ °-:'i’7—°5 H" b! 5- O 0 || || HO-P—O—P —o |_ |_ o o m ADP 2' o 0 II II Ho—If—o—rf—o m 0' 0' ADP2’ ©1lionization o o H+ + -o_.'='_o_.'='_o m ('3' cl)" ADP3'" ATP4' + H20 —> ADP 3' + P?" + H"' AG") = -30.5 kJ/mol TABLE 13—5 Adenine Nucleotide, Inorganic Phosphate, and Phosphocreatine Concentrations in Some Cells Concentration (mM)* ATP ADPT AMP P,- PCr Rat hepatocyte 3.38 1.32 0.29 4.8 0 Rat myocyte 8.05 0.93 0.04 8.05 28 Rat neuron 2.59 0.73 0.06 2.72 4.7 Human erythrocyte 2.25 0.25 0.02 1.65 0 E. coli cell 7.90 1.04 0.82 7.9 0 *For erythrocytes the concentrations are those of the cytosol (human erythrocytes lack a nucleus and mitochondria). In the other types of cells the data are for the entire cell contents, although the cytosol and the mitochondria have very dif— ferent concentrations of ADP. PCr is phosphocreatine, discussed on p. 505. TThis value reflects total concentration; the true value for free ADP may be much lower (see Box 13—1). Adenine 'O—P—O—P—O—P—O MgATP 2' \ Adenine || 'O—P—O—P—O MgADP' \ \ i P H20 0 O / 0/ \0— -— 0_c/ o H ta utomerization —o_ c/ o \c/ hydrolysis i \c/ “~— \c/ u Pi II I CH2 CH2 CH3 PEP Pyruvate Pyruvate (enol form) (keto form) PEP3' + H20 —> pyruvate' + P?" AG’O = -61.9 kJ/mol \P/ / \ 5— 5- resonance 0 0 0— O OH 0‘ IO \ / \ / V"? stabilization 1 C C C 2C|HOH Pi CIHOH H+ CIHOH I 71, I Z = I 3CH2 CH2 — CH2 | H 20 | I I I I ' ionization _O_IIJ=O hydrolySIs _o_l|,=o _o_li’=o 0— 0— 0— 1,3—Bisphosphoglycerate 3-PhoSphoglyceric acid 3-Phosphoglycerate 1,3-Bisphosphoglycerate4' + H20 —> 3-phosphoglycerate3' + P?" + H"' A6” = —49.3 kJ/mol c00' c00' coo. | | (3,. I i: H Cr'z CI": Cf” 'o—P—N—c—N—CH3 —‘-T HzN—C—N—CHg <—> EC=N—CH3 I_ hydrolysis res?!1an.ce H Nay 5+ 0 +NH2 Pi +NH2 stabilization 25+ PhOSphocreatine Creatine Phosphocreatinez' + H20 —> creatine + P?- A6” = —43.0 kJ/mol Extra stabilization of oxygen ester resonance Oxygen ester _ resonance 5 yo stabilization #0 CH3—c (—) { AG for \ ~0—R thioester hydrolysis Free energy, G AG for oxygen ester hydrolysis CH3 /0 —C\ Acetyl-CoA S-COA H20 hydrolysis CoASH Acetic acid /0 CH3—C\ o H ionization l “+- resonance stabilization Acetyl-CoA + H20 —> acetate' + CoA + H+ AG’O = —31.4 kJ/mol 1 :i. :21 Standard Free Energies ef Hydmlyeie ef Seme Pheepheryleted Cemp-eunde and Aeetyl-Eee {e Thin-ester} at?“ {Hfmelill {kcalirnel} Phespheenelpyruuete 51.9 14.3 1.3-biepheepheglyeerete [—r 3-pheepheglyeerete + P} 4119.3 —11.8 Pheepheereatine 413.12] —1U.3 ADP [a AMP + P.} —32.8 —?_E FILTF' {—1- ADP I P} 30.5 13 ATP {4 AMP + PP} 415.6 —1|CJ.E AMP [—2- edeneeine + P.) — 1151.2 —3.-!1 PF. {—3- EP} —19 —£1.fl Glueeee 1-pheephete EELS 5J3 Frueteee fi-pheephete — 15.13;I —3-E Glueeee Etheephete —13.8 —3.3 Glycerel l-pheephete —9.2 —E_E Aeetyl-Cefl. —31.4 —?.5 Sauce: Data rrlt_'us’tl_'..I Trem Jeneke, WP. {193%} in Hendb-eek cu‘ Efechemrsmr and Mefeeufar Heme-lg}; 3rd edn {Fem-Ian- GEL. e-:|.3. PhyEI-ea! and Shawn! flare. 'u'e-I. I- pp. 296—334. CPI: Preee. Bee-e Helen. FL. (a) Written as a one-step reaction C00' C00— + | + | HBN—(IjH ATP ADP + P; H3N_(|:|-| (EH2 + NH3 LL) EH2 i'“ i": C C / \ _ / \ o o 0 NH: Glutamate Glutamine ATP NH3 ADP CIOO' .|. G) “3”?” (9 cle P‘ ‘1”2 C / 0/ \O 0 \P/ _ / \ _ 0 O Enzyme-bound glutamyl phosphate (b) Actual two-step reaction Three positions on ATP for attack by the nucleophile R186 R186 R186 R180 ‘1? ‘u’ ‘u’ ‘u’ R180—IID—o- R‘BO—T—O—T—O‘ Rwo—Ir—o m 0‘ 0" 0‘ O“ + + + ADP AMP PPi Phosphoryl Pyrophosphoryl Adenylyl transfer transfer transfer (a) (b) (c) 0000 a? || || || CHHICHEM —CR | {J—P—G— |‘—D—l’—{)— Rzi b 0 A) 0 LL) P'Pi .—.‘“ 2Pi. lIJUTgHIHL' phwflplmaulwase {in UHSECthm—CR El} fl—P—fl m Adenine 31 PHJmituyl-adenylata UDASH Coenzyme A U Cr 1 6;? || _ LHEEUHEh‘; —'l3Max + 0—1?—U Ademne S—CflA G Palmitnyl-UDA ADIP Overall reaction: Palmitate + ATP + flnASII —:~ palmitnyl—CnA + AMP + 2H AG” = —32.5 kaml ...
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This note was uploaded on 12/02/2009 for the course CH 53890 taught by Professor Raymonds during the Spring '09 term at University of Texas at Austin.

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Lecture21-Ch13-1-Oct29_2007 - Photosynthetic autotruphs...

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