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Chem Picnic Saturday May 13 2-6 pm Fairhaven Park Sign up in the Chem office. "Cumulative Environmental Effects of Oil and Gas Activities on Alaska\'s North Slope". Dr. Gordon Orians, Emertius Professor of the University of Washington Monday May 15 at 6:30 pm in Fraser Hall, Room 4.

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slide1

Chem Picnic Saturday May 13

2-6 pm Fairhaven Park

Sign up in the Chem office

slide2

"Cumulative Environmental Effects of Oil and Gas

Activities on Alaska\'s North Slope".

Dr. Gordon Orians, Emertius Professor of the University

of Washington

Monday May 15 at 6:30 pm in Fraser Hall, Room 4.

slide10

Figure 17-30 VVp. 451 in VVPThe reaction mechanism of alcohol dehydrogenase involves direct hydride transfer of the pro-R hydrogen of NADH to the re face of acetaldehyde.(p. 451 VVP)

Page 606

slide11

Pyruvate Dehyrdogenase Reaction:

Pyruvate + Coenzyme A + NAD+

Acetyl CoA + CO2 + NADH

TCA Cycle :

AcetylCo A + 3 NAD+ + FAD + GDP + Pi

2 CO2 + 3 NADH + FADH2 + GTP + CoA

slide15

Figure 21-3a Electron micrographs of the E. coli pyruvate dehydrogenase multienzyme complex. (a) The intact complex. (b) The dihydrolipoyl transacetylase (E2) “core” complex.

Noncovalent assn. of prtoeins catalyzing sequential steps

figure 21 4 structural organization of the e coli pdc
Figure 21-4 Structural organization of the E. coli PDC.

Even more complex in yeast and mammals!

12 dihydrolypoyl

dehydrogenase (E3)

(as dimers)

24 subunits

Page 769

PDH: 24

Subunits (E1)

(as dimers)

E2 Dihydrolypoly

transacetlyase core

(trimers)

a+b

slide18

Figure 21-2 Chemical

structure of acetyl-CoA.

G = -31.5 kJ/mol

Page 768

slide20

Where have you seen this reaction

before?

Rxn 1: Pyruvate

Decarboxylase!

Electron sink nature

of TPP delocalizes

the negative charge

on the carbanion

intermediate

slide21

Rxn 2: Transfer

of acetyl group to

Lipoamide

Attack of carbanion

on disulfide followed

by TPP elimination

slide23

Rxn 4:

reoxidation

of LA

slide25

Swings around

among active sites

slide27

Figure 21-16 The reaction transferring an electron pair from dihydrolipoyl dehydrogenase’s (E3)redox-active disulfide in its reduced form to the enzyme’s bound flavin ring.

FAD acts like an electron conduit between reduced disulfide and NAD+.

Page 780

figure 21 17a factors controlling the activity of the pdc a product inhibition
Figure 21-17a Factors controlling the activity of the PDC. (a) Product inhibition.

Page 781

Products drive the red reactions backwards!

slide29
Figure 21-17b Factors controlling the activity of the PDC.(b) Covalent modification in the eukaryotic complex.

Page 781

slide30

Fig 16-14

VVP p 486

slide31

Fig 16-2

VVP p 468

slide33

Fig 16-5

VVP p 472

slide34

VVP p 480

H

R

R

H

+ 2H+ + 2e-

See Fig 17-10 VVP p 503

slide35

Fig 16-2

VVP p 468

slide36

Fig 16-9

VVP p 477

slide37

Fig 16-9

VVP p 477

slide39

Reaction occurs only at this bond

Citrate is PROCHIRAL.

VVP p 481

slide41

Fig 16-10

VVP p 477

slide42

VVP p 478

Mechanism: see Pyruvate DH

slide43

Fig 16-11

VVP p 479

slide44

In the absence of succinyl-CoA, the synthetase catalyzes the

transfer of the -phosphate group from ATP to ADP, which

suggests that the enzyme has a phospho-intermediate.

VVP p 479

slide45

VVP p 480

H

R

R

H

+ 2H+ + 2e-

See Fig 17-10 VVP p 503

slide48

Fig 17-23

VVP p 521

slide52

Inh: F-

VVP p. 398

slide53

Fig 14-23

VVP

WHY?

ATP inhibition also relieved by ADP…Citrate also acts as an inhibitor.

slide54

Resting muscle

Active muscle

Fig 14-25

VVP

slide58

Fig 17-7

VVP p 499

slide60

Fig 17-8

VVP p 501

slide68

Fig 17-17

VVP p 510

Cytochrome c

oxidase

slide69

Fig 17-16

VVP p 509

Beef heart

cytochrome

oxidase.

slide72

Fig 17-19

VVP p 514

slide73

Fig 17-20

VVP p 515

slide74

Fig 17-20

VVP p 515

slide75

Fig 17-21

VVP p 516

slide76

Fig 17-18

VVP p 512

slide77

Fig 17-22

VVP p 519

slide79

Fig 17-23

VVP p 521

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