Electrons from food 2e Energy released Product for ATP ......Copyright © The McGraw-Hill Companies,...

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Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Product Enzyme NAD + NAD + NAD NAD 2e H + +H + Energy-rich molecule NAD + 1. Enzymes that use NAD + as a cofactor for oxidation reactions bind NAD + and the substrate. 2. In an oxidation–reduction reaction, 2 electrons and a proton are transferred to NAD + , forming NADH. A second proton is donated to the solution. 3. NADH diffuses away and can then donate electrons to other molecules. Reduction Oxidation H H H H H H H H 1 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. 2e Electrons from food High energy Low energy 2H + 1 / 2O 2 Energy released for ATP synthesis H 2 O 2 2H H + Reduction Oxidation Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. 3 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. – ADP Enzyme Enzyme – ATP PEP Adenosine Pyruvate P P P P P Adenosine P 4 Outer mitochondrial membrane Intermembrane space Mitochondrial matrix CO2 ATP H2O FAD O2 Inner mitochondrial membrane Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. ATP e Electron Transport Chain Chemiosmosis ATP Synthase e H + e NAD + NADH Glycolysis Pyruvate Glucose Pyruvate Oxidation Acetyl-CoA NADH Krebs Cycle CO2 ATP NADH FADH2 5 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Glycolysis NADH Pyruvate Oxidation ATP Electron Transport Chain Chemiosmosis Krebs Cycle 6-carbon sugar diphosphate NAD+ NAD+ Priming Reactions Cleavage Oxidation and ATP Formation STEPS C and D NADH NADH P P P P STEP A ATP ATP ADP ADP STEP B 3-carbon sugar phosphate 3-carbon sugar phosphate Pi Pi ADP ADP ATP ATP ATP ADP ADP ATP 3-carbon pyruvate 3-carbon pyruvate 6-carbon glucose (Starting material) Glycolysis begins with the addition of energy. Two high- energy phosphates (P) from two molecules of ATP are added to the 6-carbon molecule glucose, producing a 6-carbon molecule with two phosphates. Then, the 6-carbon molecule with two phosphates is split in two, forming two 3-carbon sugar phosphates. An additional Inorganic phosphate ( Pi ) is incorporated into each 3-carbon sugar phosphate. An oxidation reaction converts the two sugar phosphates into intermediates that can transfer a phosphate to ADP to form ATP. The oxidation reactions also yield NADH giving a net energy yield of 2 ATP and 2 NADH. 6

Transcript of Electrons from food 2e Energy released Product for ATP ......Copyright © The McGraw-Hill Companies,...

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    Product

    Enzyme

    NAD+

    NAD+ NAD NAD

    2e–

    H+

    +H+

    Energy-rich molecule

    NAD+

    1. Enzymes that use NAD+

    as a cofactor for oxidation reactions bind NAD+ and the substrate.

    2. In an oxidation–reduction reaction, 2 electrons and a proton are transferred to NAD+, forming NADH. A second proton is donated to the solution.

    3. NADH diffuses away and can then donate electrons to other molecules.

    Reduction

    Oxidation

    H H

    H H H H

    H H

    1

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    2e– Electrons from food

    High energy

    Low energy

    2H+ 1 / 2 O2

    Energy released for ATP synthesis

    H2O

    2

    2H H+

    Reduction

    Oxidation

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    3

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    – ADP

    Enzyme Enzyme

    – ATP

    PEP

    Adenosine

    Pyruvate

    P

    P P

    P

    P

    Adenosine

    P

    4

    Outer mitochondrial

    membrane

    Intermembrane space

    Mitochondrial matrix

    CO2

    ATP H2O FAD O2

    Inner mitochondrial

    membrane

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    ATP

    e–

    Electron Transport Chain

    Chemiosmosis ATP Synthase

    e–

    H+

    e– NAD+

    NADH

    Glycolysis

    Pyruvate

    Glucose

    Pyruvate Oxidation

    Acetyl-CoA NADH

    Krebs Cycle

    CO2

    ATP

    NADH

    FADH2

    5

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    Glycolysis

    NADH

    Pyruvate Oxidation

    ATP

    Electron Transport Chain Chemiosmosis

    Krebs Cycle

    6-carbon sugar diphosphate

    NAD+ NAD+

    Pri

    min

    g R

    eact

    ion

    s C

    leav

    age

    Oxi

    dat

    ion

    an

    d A

    TP

    Fo

    rmat

    ion

    STEPS C and D

    NADH NADH

    P P

    P P

    STEP A

    ATP ATP

    ADP ADP

    STEP B

    3-carbon sugar phosphate

    3-carbon sugar phosphate

    Pi Pi

    ADP ADP

    ATP ATP

    ATP

    ADP ADP

    ATP

    3-carbon pyruvate

    3-carbon pyruvate

    6-carbon glucose (Starting material)

    Glycolysis begins with the addition of energy. Two high- energy phosphates (P) from two molecules of ATP are added to the 6-carbon molecule glucose, producing a 6-carbon molecule with two phosphates.

    Then, the 6-carbon molecule with two phosphates is split in two, forming two 3-carbon sugar phosphates.

    An additional Inorganic phosphate ( Pi ) is incorporated into each 3-carbon sugar phosphate. An oxidation reaction converts the two sugar phosphates into intermediates that can transfer a phosphate to ADP to form ATP. The oxidation reactions also yield NADH giving a net energy yield of 2 ATP and 2 NADH.

    6

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    NADH NAD+ NADH Pi NAD+

    Glucose Hexokinase

    Phosphofructokinase

    Glucose 6-phosphate

    Fructose 6-phosphate

    Fructose 1,6-bisphosphate Isomerase Aldolase

    Pyruvate Pyruvate

    Enolase

    Pyruvate kinase

    AD P

    10

    Glu

    cose

    Gly

    cera

    ldeh

    yde

    3-p

    ho

    sph

    ate

    Pyr

    uva

    te

    Glycolysis: The Reactions Glycolysis NADH

    Pyruvate Oxidation

    H2O

    ATP

    ADP

    Electron Transport Chain Chemiosmosis

    Krebs Cycle

    ATP

    ATP

    Phosphoglucose isomerase

    Glyceraldehyde 3- phosphate (G3P)

    Dihydroxyacetone phosphate

    1. Phosphorylation of glucose by ATP.

    2–3. Rearrangement, followed by a second ATP phosphorylation.

    4–5. The 6-carbon molecule is split into two 3-carbon molecules—one G3P, another that is converted into G3P in another reaction.

    6. Oxidation followed by phosphorylation produces two NADH molecules and two molecules of BPG, each with one high-energy phosphate bond.

    7. Removal of high-energy phosphate by two ADP molecules produces two ATP molecules and leaves two 3PG molecules.

    8–9. Removal of water yields two PEP molecules, each with a high-energy phosphate bond.

    10. Removal of high-energy phosphate by two ADP molecules produces two ATP molecules and two

    1,3-Bisphosphoglycerate (BPG)

    1,3-Bisphosphoglycerate (BPG)

    Glyceraldehyde 3-phosphate

    dehydrogenase

    Pi

    ADP

    Phosphoglycerate kinase

    ADP

    ATP

    3-Phosphoglycerate (3PG)

    3-Phosphoglycerate (3PG)

    2-Phosphoglycerate (2PG)

    2-Phosphoglycerate (2PG)

    H2O

    ATP

    Phosphoenolpyruvate (PEP)

    Phosphoenolpyruvate (PEP)

    ADP ADP

    ATP ATP

    Ph

    osp

    ho

    eno

    l-

    pyr

    uva

    te

    3-P

    ho

    sph

    o-

    gly

    cera

    te

    1,3-

    Bis

    ph

    osp

    ho

    - g

    lyce

    rate

    G

    luco

    se

    6-p

    ho

    sph

    ate

    Fru

    cto

    se

    6-p

    ho

    sph

    ate

    Fru

    cto

    se

    1,6-

    bis

    ph

    osp

    hat

    e D

    ihyd

    roxy

    acet

    on

    e P

    ho

    sph

    ate

    2-P

    ho

    sph

    o-

    gly

    cera

    te

    CH2OH O

    CH2 O O P

    CH2 O O P CH2OH

    O CH2 CH2 O O P P

    CHOH H C O CH2 O P

    C O O CH2 P CH2OH

    CHOH O C O CH2 O

    P P

    CHOH O–

    C O CH2 O P

    H C O O–

    C O CH2OH

    P

    C O O–

    C O CH2

    P

    C O O–

    C O CH3

    8

    9

    10

    7

    4 5

    3

    2

    1

    6

    Phosphoglyceromutase

    7

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    Without oxygen

    NAD+

    O2 NADH

    ETC in mitochondria

    Acetyl-CoA

    Ethanol

    NAD+

    CO2

    NAD+

    H2O

    Lactate

    Pyruvate

    Acetaldehyde NADH

    NADH

    With oxygen

    Krebs Cycle

    8

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    Glycolysis

    Pyruvate Oxidation

    NADH

    Krebs Cycle

    Electron Transport Chain Chemiosmosis

    Pyruvate Oxidation: The Reaction

    NAD+ CO2

    CoA

    Acetyl Coenzyme A

    Pyruvate

    Pyr

    uva

    te

    Ace

    tyl C

    oen

    zym

    e A

    O

    CH 3

    C

    O–

    C O ⎯⎯

    ⎯⎯

    S CoA

    CH3

    O C ⎯⎯

    NADH

    9

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    SEGMENT A Pyruvate from glycolysis is oxidized into an acetyl group that feeds into the citrate cycle. 2-C acetyl group combines with 4-C oxaloacetate to produce the 6-C compound citrate.

    SEGMENT B Oxidation reactions produce NADH. The loss of two CO2's leaves a new 4-C compound. 1 ATP is directly generated for each acetyl group fed in.

    CoA- (Acetyl-CoA)

    CoA

    4-carbon molecule

    (oxaloacetate) 6-carbon molecule

    (citrate)

    NAD +

    NADH

    CO2

    5-carbon molecule

    NAD+

    NADH

    CO2 4-carbon molecule

    ADP + P

    Krebs Cycle

    FAD

    FADH2

    4-carbon molecule

    NAD+

    NADH

    SEGMENT C Two additional oxidations generate another NADH and an FADH2 and regenerate the original 4-C oxaloacetate. ATP

    Glycolysis

    Pyruvate Oxidation

    Electron Transport Chain Chemiosmosis

    NADH

    FADH2

    Krebs Cycle

    ATP

    SEGMENT A

    SEGME

    NT B

    SE

    GM

    EN

    T C

    4-carbon molecule

    10

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    Glycolysis

    NADH

    F ADH2

    Pyruvate Oxidation

    ATP

    Krebs Cycle: The Reactions

    Citrate synthetase

    NAD+

    NADH

    H2O

    NAD+

    NADH

    CO2

    F AD Isocitrate dehydrogenase

    Fumarase

    CoA-SH 1

    2

    Aconitase 3

    4

    8

    9

    7

    CoA-SH

    NAD+

    CO2

    5

    6

    NADH

    CoA-SH

    GDP + Pi

    Acetyl-CoA

    CH3 — C — S

    O CoA —

    Krebs Cycle

    Malate dehydrogenase

    α-Ketoglutarate dehydrogenase

    Succinyl-CoA synthetase

    GTP

    ATP

    ADP

    Succinate dehydrogenase

    FADH2

    8–9. Reactions 8 and 9: Regeneration of oxaloacetate and the fourth oxidation

    7. Reaction 7: The third oxidation

    6. Reaction 6: Substrate-level phosphorylation

    5. Reaction 5: The second oxidation

    4. Reaction 4: The first oxidation

    2–3. Reactions 2 and 3: Isomerization

    1. Reaction 1: Condensation

    Electron T ransport Chain Chemiosmosis

    Oxaloacetate (4C)

    CH2

    O ═ C

    COO—

    COO—

    Citrate (6C)

    HO — C — COO—

    COO—

    COO—

    CH2

    CH2

    Isocitrate (6C)

    HC — COO—

    COO—

    COO—

    CH2

    HO — CH

    α-Ketoglutarate (5C)

    CH2

    COO—

    COO—

    CH2

    C — O

    Succinyl-CoA (4C)

    CH2

    COO—

    S — CoA

    CH2

    C ═ O

    Succinate (4C)

    COO—

    CH2

    COO—

    CH2

    Fumarate (4C)

    HC

    CH

    COO—

    COO—

    Malate (4C)

    HO — CH

    COO—

    CH2

    COO—

    11

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    Mitochondrial matrix

    NADH + H+ ADP + Pi

    H2O

    H+ H+

    2H+ + 1 / 2 O2

    Glycolysi s

    Pyruvate Oxidatio n

    2

    Krebs Cycle ATP

    Electron Transport Chain Chemiosmosis

    NADH dehydrogenase bc1 complex Cytochrome

    oxidase complex

    FAD

    Inner mitochondrial membrane

    Intermembrane space

    a. The electron transport chain

    ATP synthase

    ATP

    b. Chemiosmosis

    NAD+

    Q

    C

    e–

    FADH2

    H+ H+

    H+ H+

    e– 2 2 e– 2 2

    12

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    ADP+Pi

    Catalytic head

    Stalk

    Rotor

    H+

    H+

    Mitochondrial matrix

    Intermembrane space

    H+ H+

    H+

    H+ H+

    ATP

    13

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    H2O

    CO2

    CO2

    H+

    H+

    2H+ +

    1 / 2 O2

    H+

    e-

    H+

    32 ATP Krebs Cycle

    2 ATP

    NADH

    NADH

    FADH2

    NADH

    Pyruvate Oxidation

    Acetyl-CoA

    e-

    Q C

    e-

    Glycolysis

    Glucose

    Pyruvate 2 ATP

    14

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    Chemiosmosis

    Chemiosmosis

    2 6

    2 4

    6 18

    2

    2

    2 6 NADH

    NADH

    NADH

    Total net ATP yield = 38 (36 in eukaryotes)

    ATP

    ATP

    ATP

    ATP

    ATP

    ATP

    Krebs Cycle

    Pyruvate oxidation

    FADH2

    Glycolysis 2

    Glucose

    Pyruvate

    ATP

    15

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    Glucose

    Acetyl-CoA

    Fructose 6-phosphate

    Fructose 1,6-bisphosphate

    Pyruvate

    Pyruvate Oxidation

    Krebs Cycle

    Electron Transport Chain and

    Chemiosmosis

    Citrate

    ADP

    ATP

    NADH

    Inhibits

    Inhibits

    Activates

    Inhibits

    Phosphofructokinase

    Pyruvate dehydrogenase

    Glycolysis

    16

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    CO2

    2 Acetaldehyde

    2 AD P

    2 Lactate

    Alcohol Fermentation in Yeast

    2 ADP

    Lactic Acid Fermentation in Muscle Cells

    2 NAD+

    2 NAD+

    2 NADH

    2 NADH

    2 ATP

    2 ATP

    C O

    C O

    O–

    CH3

    C O

    H

    CH3

    C O

    C O

    CH3

    O–

    CH3

    H C OH

    C O

    O–

    H

    2 Ethanol

    H C OH

    CH3

    17

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    Cell building blocks

    Deamination β-oxidation Glycolysis

    Oxidative respiration

    Ultimate metabolic products

    Acetyl-CoA

    Pyruvate

    Macromolecule degradation

    Krebs Cycle

    Nucleic acids Polysaccharides

    Nucleotides Amino acids Fatty acids Sugars

    Proteins Lipids and fats

    NH3 H2O CO2

    18

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    Urea

    NH3

    19