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The First Law of Thermodynamics • According to the first law of thermodynamics, the energy of the universe is constant: – Energy can be transferred and transformed, but it cannot be created or destroyed • The first law is also called the principle of conservation of energy Copyright © 2008 Pearson Education, Inc., publishing as Pearson Benjamin Cummings The Second Law of Thermodynamics During every energy transfer or transformation, some energy is unusable, and is often lost as heat According to the second law of thermodynamics: – Every energy transfer or transformation increases the entropy (disorder) of the universe Copyright © 2008 Pearson Education, Inc., publishing as Pearson Benjamin Cummings Fig. 8-6 Free energy Reactants Energy Products Amount of energy released (∆G < 0) Progress of the reaction (a) Exergonic reaction: energy released Free energy Products Energy Reactants Amount of energy required (∆G > 0) Progress of the reaction (b) Endergonic reaction: energy required Fig. 8-8 Adenine Phosphate groups Ribose Fig. 8-9 P P P Adenosine triphosphate (ATP) H2O Pi + Inorganic phosphate P P + Adenosine diphosphate (ADP) Energy Fig. 8-10 NH2 Glu Glutamic acid NH3 + Glu ∆G = +3.4 kcal/mol Glutamine Ammonia (a) Endergonic reaction 1 ATP phosphorylates glutamic acid, making the amino acid less stable. P + Glu ATP Glu + ADP NH2 2 Ammonia displaces the phosphate group, forming glutamine. P Glu + NH3 Glu + Pi (b) Coupled with ATP hydrolysis, an exergonic reaction (c) Overall free-energy change Fig. 8-12 ATP + H2O Energy from catabolism (exergonic, energy-releasing processes) ADP + P i Energy for cellular work (endergonic, energy-consuming processes) Fig. 9-6-3 Electrons carried via NADH and FADH2 Electrons carried via NADH Citric acid cycle Glycolysis Pyruvate Glucose Oxidative phosphorylation: electron transport and chemiosmosis Mitochondrion Cytosol ATP ATP ATP Substrate-level phosphorylation Substrate-level phosphorylation Oxidative phosphorylation • Oxidative phosphorylation accounts for almost 90% of the ATP generated by cellular respiration • A smaller amount of ATP is formed in glycolysis and the citric acid cycle by substrate-level phosphorylation Copyright © 2008 Pearson Education, Inc., publishing as Pearson Benjamin Cummings Fig. 9-7 Enzyme Enzyme ADP P Substrate + Product ATP Fig. 9-8 Energy investment phase Glucose 2 ADP + 2 P 2 ATP used P 4 ATP formed Energy payoff phase 4 ADP + 4 2 NAD+ + 4 e– + 4 H+ 2 NADH + 2 H+ 2 Pyruvate + 2 H2O Net Glucose 4 ATP formed – 2 ATP used 2 NAD+ + 4 e– + 4 H+ 2 Pyruvate + 2 H2O 2 ATP 2 NADH + 2 H+ Fig. 9-10 CYTOSOL MITOCHONDRION NAD+ NADH + H+ 2 1 Pyruvate Transport protein 3 CO2 Coenzyme A Acetyl CoA Fig. 9-11 Pyruvate CO2 NAD+ CoA NADH + H+ Acetyl CoA CoA CoA Citric acid cycle 2 CO2 FADH2 3 NAD+ 3 NADH FAD + 3 H+ ADP + P ATP i Fig. 9-13 NADH 50 2 e– NAD+ FADH2 2 e– 40 FMN FAD Multiprotein complexes FAD Fe•S Fe•S Q Cyt b 30 Fe•S Cyt c1 I V Cyt c Cyt a Cyt a3 20 10 0 2 e– (from NADH or FADH2) 2 H+ + 1/2 O2 H2O Fig. 9-14 INTERMEMBRANE SPACE H+ Stator Rotor Internal rod Catalytic knob ADP + P i ATP MITOCHONDRIAL MATRIX Fig. 9-16 H+ H+ H+ H+ Protein complex of electron carriers Cyt c V Q FADH2 NADH ATP synthase FAD 2 H+ + 1/2O2 NAD+ H2O ADP + P i (carrying electrons from food) ATP H+ 1 Electron transport chain Oxidative phosphorylation 2 Chemiosmosis Fig. 9-17 Electron shuttles span membrane CYTOSOL 2 NADH 6 NADH 2 NADH Glycolysis 2 Pyruvate Glucose MITOCHONDRION 2 NADH or 2 FADH2 2 Acetyl CoA + 2 ATP Maximum per glucose: 2 FADH2 Citric acid cycle Oxidative phosphorylation: electron transport and chemiosmosis + 2 ATP + about 32 or 34 ATP About 36 or 38 ATP Fig. 9-18a 2 ADP + 2 P Glucose i 2 ATP Glycolysis 2 Pyruvate 2 NAD+ 2 Ethanol (a) Alcohol fermentation 2 NADH + 2 H+ 2 CO2 2 Acetaldehyde Fig. 9-18b 2 ADP + 2 Glucose P i 2 ATP Glycolysis 2 NAD+ 2 Lactate (b) Lactic acid fermentation 2 NADH + 2 H+ 2 Pyruvate Fig. 9-19 Glucose CYTOSOL Glycolysis Pyruvate No O2 present: Fermentation O2 present: Aerobic cellular respiration MITOCHONDRION Ethanol or lactate Acetyl CoA Citric acid cycle Fig. 9-20 Proteins Carbohydrates Amino acids Sugars Fats Glycerol Glycolysis Glucose Glyceraldehyde-3- NH3 P Pyruvate Acetyl CoA Citric acid cycle Oxidative phosphorylation Fatty acids Fig. 10-3 Leaf cross section Vein Mesophyll Stomata Chloroplast CO2 O2 Mesophyll cell Outer membrane Thylakoid Stroma Granum Thylakoid space Intermembrane space Inner membrane 1 µm 5 µm Fig. 10-4 Reactants: Products: 12 H2O 6 CO2 C6H12O6 6 H2O 6 O2 Fig. 10-5-4 CO2 H2O Light NADP+ ADP + P i Light Reactions Calvin Cycle ATP NADPH Chloroplast O2 [CH2O] (sugar) Fig. 10-7 Light Reflected light Chloroplast Absorbed light Granum Transmitted light Fig. 10-9 RESULTS Chlorophyll a Chlorophyll b Carotenoids (a) Absorption spectra 400 500 600 700 Wavelength of light (nm) (b) Action spectrum Aerobic bacteria Filament of alga (c) Engelmann’s experiment 400 500 600 700 Fig. 10-13-5 4 Primary acceptor 2 H+ + 1/ O 2 2 e– H2O Primary acceptor 2 Fd e– Pq 7 e– Cytochrome complex 8 e– NADP+ reductase 3 Pc e– e– P700 5 P680 Light 1 Light 6 ATP Pigment molecules Photosystem II (PS II) Photosystem I (PS I) NADP+ + H+ NADPH Fig. 10-15 Primary acceptor Primary acceptor Fd Fd Pq NADP+ reductase Cytochrome complex NADPH Pc Photosystem I Photosystem II ATP NADP+ + H+ Fig. 10-16 Mitochondrion Chloroplast MITOCHONDRION STRUCTURE CHLOROPLAST STRUCTURE H+ Intermembrane space Inner membrane Diffusion Electron transport chain Thylakoid space Thylakoid membrane ATP synthase Stroma Matrix Key ADP + P [H+] Higher Lower [H+] i H+ ATP Fig. 10-17 STROMA (low H+ concentration) Cytochrome complex Photosystem II 4 H+ Light Photosystem I Light Fd NADP+ reductase H2O THYLAKOID SPACE (high H+ concentration) 1 e– Pc 2 1/ 2 NADP+ + H+ NADPH Pq e– 3 O2 +2 H+ 4 H+ To Calvin Cycle Thylakoid membrane STROMA (low H+ concentration) ATP synthase ADP + Pi ATP H+ Fig. 10-18-3 Input 3 CO2 (Entering one at a time) Phase 1: Carbon fixation Rubisco 3 P Short-lived intermediate 3 P Ribulose bisphosphate (RuBP) P 6 P 3-Phosphoglycerate P 6 ATP 6 ADP 3 ADP 3 Calvin Cycle 6 P P 1,3-Bisphosphoglycerate ATP 6 NADPH Phase 3: Regeneration of the CO2 acceptor (RuBP) 6 NADP+ 6 Pi P 5 G3P 6 P Glyceraldehyde-3-phosphate (G3P) 1 Output P G3P (a sugar) Glucose and other organic compounds Phase 2: Reduction Fig. 10-19 The C4 pathway C4 leaf anatomy Photosynthetic cells of C4 plant leaf Mesophyll cell Mesophyll cell CO2 PEP carboxylase Bundlesheath cell Oxaloacetate (4C) Vein (vascular tissue) PEP (3C) ADP Malate (4C) Stoma Bundlesheath cell ATP Pyruvate (3C) CO2 Calvin Cycle Sugar Vascular tissue Fig. 10-20 Sugarcane Pineapple C4 CAM CO2 Mesophyll cell Bundlesheath cell Organic acid CO2 1 CO2 incorporated into four-carbon organic acids (carbon fixation) CO2 Calvin Cycle Night Organic acid CO2 2 Organic acids release CO2 to Calvin cycle Day Calvin Cycle Sugar Sugar (a) Spatial separation of steps (b) Temporal separation of steps