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Chapter 4. Biological Oxidation. Intredction ATP oxidative phosphorylation Oxidation not producing ATP. introduction  biological oxidation

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slide1

Chapter 4. Biological Oxidation

Intredction

ATP

oxidative phosphorylation

Oxidation not producing ATP

slide2
introduction

biological oxidation

oxidation run in living body, detailedly, the process which nutrient substance, such as saccharides, lipids, and proteins are oxidized into water and carbon dioxide, and simultaneouslyproduce energy.

Nutrient + O2 H2O + CO2 + energy

ATP + heat

forms of oxidoreduction in biological oxidation
oxidizing reaction

loss of electrons

dehydrogenation

addation of oxygen

reduction reaction

Gain eletrons

Addation of hydrogen

Deoxygenation

+H

+e

[O]

[R]

-e

-H

+O

Forms ofoxidoreductionin biological oxidation
slide5

glucose

fatty acid + Glycerol

amino acids

General course of biological oxidation

glucogen

triglyceride

protein

AcetylCoA

TAC

ADP+Pi

ATP

CO2

H2O

2H

respiratory chain

slide6

Energy of reaction

G < 0 spontaneous

G = 0equilibrium

G > 0non-spontaneous

G1

G2

G = G2-G1

G0’= - 2.303 R T log Keg = - n F E0’

slide11

GDP GTP

ATP + UDP ADP + UTP

CDP CTP

Transformbetween high-energy compounds

nucleoside diphosphate kinase

adenylate kinase

ADP + ADP  ATP + AMP

section 2 oxidative phosphorylation
Section 2. oxidative phosphorylation
  • Ways producing ATP:
  • substrate level phosphorylation
  • oxidative phosphorylation

substrate level phosphorylation

--formation of ATP by the way of straight transfer high-energy substrate energy to ADP.

slide14
1,3-二磷酸甘油酸 + ADP 3-磷酸甘油酸 + ATP

磷酸烯醇式丙酮酸 + ADP 丙酮酸 + ATP

琥珀酰CoA + H3PO4 + GDP 琥珀酸 + CoA-SH +

GTP

+

ADP

ATP

PK

slide15

I respiratory chain (呼吸链)

aoxidoreduction system which consists of a series of enzyme, coenzyme aligning in mitochondrial inner membrane, function as linksystem transferer of hydrogen and electron.

slide16

Mitochondria

Respiratory chain

slide17

Cytc

内外膜间隙侧

Q

I

线粒体内膜

基质侧

electron transfer in respiratory chain

e-

e-

e-

e-

e-

H2O

NADH+H+

延胡素酸

1/2O2+2H+

NAD+

琥珀酸

slide18

succinic acid oxidation respiratory chain

NADH oxidation respiratory chain

1 complex nadh q reducase

NADH

FMN,Fe-S

CoQ

(1) complexⅠ— NADH-Q reducase
  • iron-sulphur protein, Flavoprotein with FMN, 42 peptide chains, 850 kD.
  • Bind and oxidize NADH, transfer electrons to Q, release 4H+ to interspace of inner and outer membrane.
slide21

Structure of NAD+ and NADP+

R=H:NAD+; R=H2PO3:NADP+

NAD+:nicotinamide adenine dinucleotide,CoI

NADP+:nicotinamide adenine dinucleotide phosphate,CoII

slide24

Fe2+ Fe3+ + e

Fe4S4

ironsulfur protein

Fe-S

Fe2S2, Fe4S4

slide25
Ubiquinone,Q

(Coenzyme Q,CoQ) 人体中: CoQ10

  • quinones contain a polyisoprene side chain.
  • liposolubility,make it move in mitochondrial inner membrane easily.
  • the only one electron carrier without protein in respiratory chain.

slide26

2H+

FMN

Fe-S

N-2

Q

QH2

复合体Ⅰ传递电子的过程

2e-

2H+

NAD+

NADH+H+

NADH+H+

FMN

Fe2+

Q

FMNH2

Fe3+

QH2

NAD+

Q

NADH

FMN

Fe-S

slide27

(2) complexⅡ-

Succinate-CoQ reductase

  • i.e. succinate dehydrogenase, consists at list 4 peptides. Contain one FAD, two ironsulfur protein and one Cyt b560.
  • Transfer electron from succinic acid to Q, do not release H+ to the interspace.

succinic acid→FAD→Fe-S→Q。

slide28
cytochrome,Cyt 细胞色素

A、structure: colourant protein containing iron porphyrin.

B、typing: Cyta: Cytaa3

Cytb: Cytb562、Cytb566、 Cytb560

Cytc: Cytc 、 c1

C、difference:

① different side chain of iron porphyrin.

  • Different linkage form of iron porphyrin with the protein.

CytFe3+ + e  CytFe2+

slide31

(3) Complex Ⅲ Q-cytc reducase

  • i.e. cyt c reducase, consists of 11 peptide chains different, existing as a dimer. every monomer contains two cyt b (b562, b566), one cyt c1 and a iron sulphur protein.
  • Catalyze electron transfer from Q to cyt c. every two electrons’s transfering lead four proton pumped to the intermembrance space.

Cytc

QH2

b566b562Fe-Sc1

slide32

Cyt c

Complex Ⅲ

slide33

Electron transfering process in complexⅢ

first time oxidation of QH2

secondary time oxidation of QH2

Cytc

Cytc

2H+

2H+

Cytc1

Cytc1

Fe-S

Fe-S

e-

e-

bL

bL

e-

e-

QH2

Q

QH2

Q

bH

bH

Q

Q

QH2

Q

2H+

slide34

(4) complex Ⅳ

Cyt c oxidase

  • Dimer. Every monomer consists of 13 peptide chains different, as 3 subunits: I include 2 heme(a,a3),a cuproprotein (CuB);Ⅱinclude a dikaryon center formed by two copper ion(CuA);Ⅲ not clear
  • Cu2+ + e  Cu+

Cyt c

CuA a  a3  CuB

O2

slide35

NADH氧化呼吸链

NADHFMN(Fe-S)Qbc1caa3O2

琥珀酸氧化呼吸链

succinic acidFAD(Fe-S)Qbc1caa3O2

slide36

呼吸链

NADH + H+ + 1/2O2

NAD+ + H2O

呼吸链

FADH2 + 1/2O2

FAD + H2O

呼吸链

2H + 1/2O2

H2O

In FADH2 or NADH

overall reaction

or

further

slide37
呼吸链中电子传递体的排列顺序的确定
  • 利用脱氧胆酸处理线粒体内膜、分离出呼吸链的4种复合物,辅酶Q和细胞色素C及ATP合酶。
  • 根据标准氧还电位E0’的高低排列
  • 根据电子传递体氧化还原态时的吸收光谱变化进行检测
  • 利用阻断剂研究分析
  • 四种复合物的电子传递再造实验
ii oxidative phosphorylation
II、oxidative phosphorylation

oxidative phosphorylation refer to the ATP producing form which the reaction ADP change into ATP couple withrespiratory chain oxidation. It is main form of ATP producing in body.

slide40

energy

ATP+H2O

30.5kJ/mol

ADP + Pi

energy level diagram

Why does the reaction: ADP + Pi  ATP + H2O request a couple?

The product state(ATP+H2O) is higher energy level than reactant state(ADP + Pi). So, ADP change into ATP isn’t spontaneous process. Energy obtaining is requested for the process.

what s p o ratio what s its meaning
What’s P/O ratio?What’s its meaning?

--- number of moles of ATP produced as consuming a mole of oxygen atom in a reaction, i.e. the number of moles of phosphor cosumed when consume a mole of oxygen atom in the reaction.

slide43

1961~1978

  • What’s the way of ADPphosphorylation coupled with respiratory chain oxidation?

氧化磷酸化偶联机制有:化学物质偶联学说、构象偶联学说及化学渗透学说。目前公认度较大的是化学渗透学说。

Chemiosmotic hypothesis

  • the energy of respiratory chain oxidation change into proton gradient across the inner membrane.
  • the proton gradient drive ATP-synase produce ATP.
slide44

In electron transfer process, respiratory chain put proton to intermembrance of inner and outer membrance, result in proton concentration different of the two side of the inner membrance.

slide45

conceptual diagram of Chemiosmotic hypothesis

H+

H+

H+

H+

H+

H+

+ + + + + + + + + + + + + + + + + + +

- - - - - - - - - - - - - - -

e-

延胡素酸

H2O

NADH+H+

琥珀酸

1/2O2+2H+

NAD+

ATP

ADP+Pi

slide46

ATP synase

  • Consists of hydrophobic F0(a1b2c912)and hydrophilic F1(33).
  • When proton go straight through a,push c loop turning , and as a result, spur the F1 turning.
slide48

松开

(O)

(O)

H+

结好

(L)

H+

脱水

(T)

H+

work principle of ATP synase

Three conformations of subunit:松L,紧T,放O

Procedure of ATP production:

slide49

Ⅲ. Factors affecting oxidation phosphorylation

  • Inhibitors
  • Regulation by ADP
  • Thyroid hormone
  • Mitchondrial DNA mutation
slide50

(1)Inhibitors

  • Inhibitors of respiratory chain

blockelectron transfer of respiratory chain.

  • Uncoupler

destroy the coupling of oxidation with phosphorylation, like uncoupling protein, 2,4-dinitrophenol.

  • Inhibitors of oxidative phosphorylation

restrain the proton return to matrix side in ATP synase, like oligomycin

slide51

Blocking sites of inhibitorof respiratory chain

CO、CN-、N3-及H2S

抗霉素A

二巯基丙醇

异藤酮

粉蝶霉素A

异戊巴比妥

slide52

H+

H+

H+

Machanism of uncoupling

解偶联蛋白

H+

H+

ADP+Pi

ATP+H2O

slide53

寡霉素

inhibitory action of oligomycin

stop proton flow from F0 proton channel.

slide54
(2) regulation by ADP

main regulation factor:ADP/ATP ratio

ADP + Pi  ATP + H2O

Respiratory control ratio

离体线粒体实验,过量底物存在时,加入ADP后的耗氧速率与仅有底物时的耗氧速率之比

slide55

Na+-K+ ATP enzyme

ATP degradation

ADP/ATP

Oxidative phosphorylation

(3). Thyroid Hormone

Thyroid Hormone

甲状腺激素

slide56

(4) Mitchondrial DNA mutation

function ofmitochondrium

Mitochondrium diseases

  • all of the 13 peptides (7 peptides in NADHdehydrogenase, 1 in Cytcreducase, 3 in Cyt coxydase,2 in ATP synase coded) by Mitochondrium join in oxidative phosphorylation.
  • Mutation affectoxidative phosphorylation, ATP production decrease.
  • Naked cyclic duble helix DNA, lack of defend system and restoration system.
  • Symptoms are dependent on the degree of mutation and the different organs need for ATP.
    • Maternally inherited diseases (heritage neurosis, heritage diabetes and deafness)
  • Aging related
iv mitochondria entry and exit of molecules
IV、 Mitochondria Entry and Exit of Molecules

Mitochondrial porin, the major protein of the outer mitochondrial membrane, allows molecules less than 10 kD to pass

Inner membrance were controled by differnet transporter.

slide59

Oxidation of NADH in cytosol

  • α-glycerophosphate shuttle

(α-磷酸甘油穿梭)

  • malate-asparate shuttle

(苹果酸-天冬氨酸穿梭)

slide61

-磷酸甘油脱氢酶

-磷酸甘油脱氢酶

-glycerol phosphate shuttle

呼吸链

NADH+H+

FADH2

NAD+

FAD

slide62

3ATP

malate-asparate shuttle

aerobic dehydrogenase and oxydase
Ⅰ. aerobic dehydrogenase and oxydase

Section 3. other oxidationsystem

slide65

Ⅱ. Erzymes in peroxisome

过氧化酶体中的酶类

(1).catalase 过氧化氢酶

  • catalytic reaction: one molecule H2O2offer electron;another molecule H2O2accept electron.
  • prosthetic group: 4 heme
  • Function: wide distribution, wipe out toxical H2O2
slide66

(2). peroxidase (过氧化物酶)

  • Catalytic reaction:catalyze H2O2 straight oxidize phenols and amines
  • prosthetic group:1 heme

Protect body. glutathione peroxidase

Clinical diachorema occult blood test:

superoxide dimutase sod
Ⅲ . superoxide dimutase, ( SOD,超氧化物歧化酶)

呼吸链电子传递过程中产生超氧离子(O2-.)

  • O2-. H2O2 + .OH
  • 损伤生物膜、生成脂褐素

SOD

2O2-. + 2H+ H2O2 + O2

H2O + O2

过氧化氢酶

SOD辅基含Cu、Zn(胞液)

或Mn(线粒体)。

1 monooxygenase

RH+NADPH+H++O2 ROH+NADP++H2O

(1). monooxygenase (加单氧酶)

Ⅳ. Oxidases inmicrosome

mixedfunction oxidase(混合功能氧化酶)

or Hydroxylase(羟化酶).

Catalytic reaction:

composition: NADPH-Cytc reducase, flavoprotein(FAD), ironsulfur protein(Fe2S2)、CytP450。

function:hydroxylation羟化。胆汁酸、胆固醇的生成;药物、毒物的转化;肾上腺皮质、类固醇激素的生物合成。

slide69

mechanism

RH.P450.Fe3+

RH

H2O

ROH

2 dioxygenases

色氨酸吡咯酶 O2

(2). dioxygenases (双加氧酶)

incorporate both oxygen atoms into the substrate.

slide71
提要
  • ATP的生成主要通过氧化磷酸化。
  • 呼吸链是线粒体内膜中的一系列递氢和递电子酶及其辅酶按照一定顺序排列成的连锁性氧化还原体系。主要有两条:NADHFMN(FeS)Qbc1c aa3  O2

琥珀酸FADH(FeS)Qbc1caa3O2

  • 呼吸链的电子传递与氧化磷酸化有三处偶联:NADHQ;CtybCytc;Cytaa3O2
  • 化学渗透假说
  • 影响氧化磷酸化的因素
  • 需氧脱氢酶、氧化酶、过氧化氢酶、过氧化物酶、SOD、羟化酶及加双氧酶的作用。
slide72

选择题练习

生物氧化

slide73

1. 呼吸链存在于( )

A 细胞膜

B 线粒体外膜

C 线粒体内膜

D 微粒体

E 过氧化物酶体

slide74

2. 下列哪种物质不是NADH氧化呼吸链的组分?

A. FMN

B. FAD

C. 泛醌

D. 铁硫蛋白

E. 细胞色素c

slide75

3. ATP生成的主要方式是( )

A 肌酸磷酸化

B 氧化磷酸化

C 糖的磷酸化

D 底物水平磷酸化

E 高能化合物之间的转化

slide76

4 由琥珀酸脱下的一对氢,经呼吸链氧化可产生( )分子ATP

A 1

B 2

C 3

D 4

E 0

slide77

5 下例关于高能磷酸键的叙述,正确的是(

A 所有高能键都是磷酸键

B 高能磷酸键只存在于ATP

C 高能磷酸键仅在呼吸链中偶联

D 有ATP参与的反应也可逆向进行

E 所有的生化转变都需要ATP参与

slide78

6. 下列哪种酶以氧为受氢体催化底物氧化生成水?

A 丙酮酸脱氢酶

B 琥珀酸脱氢酶

C 黄嘌呤氧化酶

D 细胞色素c氧化酶

E SOD

slide79

7. 关于线粒体内膜外H+浓度叙述正确的是( )

A 浓度高于线粒体内

B 浓度低于线粒体内

C 可自由进入线粒体

D 进入线粒体需主动转运

E 进入线粒体需载体转运

slide80

8. 参与呼吸链电子传递的金属离子是( )

A 铁离子

B 钴离子

C 镁离子

D 锌离子

E 以上都不是

slide81

9. 呼吸链中,不具有质子泵功能的是( )

A 复合体Ⅰ

B 复合体Ⅱ

C 复合体Ⅲ

D 复合体Ⅳ

E 以上都不是

slide82

10. 关于超氧化物歧化酶,哪项是不正确的( )

A 可催化产生超氧离子

B 可消除超氧离子

C 可催化产生过氧花氢

D 含金属离子辅基

E 存在于胞液和线粒体中

slide84

12. Which one can be inhibited by CO in

respiratory chain ?

A FAD

B FMN

C Fe-S

D Cyt aa3

E Cyt c

slide85

13. Which one is uncoupler?

A CO

B piericidin A

C KCN

D 2,4-dinitrophenol

E H2S

slide86

14. The right electron tansferation sequence is ( )

A b→c→c1→aa3→O2

B c1→c→b→aa3→O2

C c→c1→b→aa3→O2

D c→b→c1→aa3→O2

E b→c1→c→aa3→O2

slide87

15. 关于ATP合成酶,叙述正确的是( )

A 位于线粒体内膜,又称复合体Ⅴ

B 由F1和F0两部分组成

C F0是质子通道

D 生成ATP的催化部位在F1的亚基上

E F1呈疏水性,嵌在线粒体内膜中

slide88

16. 关于辅酶Q, 哪些叙述是正确的?

A 是一种水溶性化合物

B 其属醌类化合物

C 可在线粒体内膜中迅速扩散

D 不参与呼吸链复合体

E 是NADH呼吸链与琥珀酸呼吸链的交汇点

slide89

17. 关于细胞色素,叙述正确的是( )

A 均以铁卟啉为辅基

B 有色

C 均为电子传递体

D 均可被氰化物抑制

E 本质是蛋白质

slide90

18. 下列物质属于高能化合物的是( )

A 乙酰辅酶A

B GTP

C 磷酸肌酸

D 磷酸二羟丙酮

E 磷酸烯醇式丙酮酸

slide91

19. Which make Fe-S as prosthetic group in the respiratory chain?

A Complex Ⅰ

B Complex Ⅱ

C Complex Ⅲ

D Complex Ⅳ

E Cyt c

slide92

20. Where does the phosphorylation couple with the oxidation and can produce ATP?

A NADH→CoQ

B CoQ→Cyt b

C CoQ→Cyt c

D FADH2→CoQ

E Cyt aa3→O2

slide93

论述题:

1 试述生物氧化与体外物质氧化的异同。

2 试述影响氧化磷酸化的因素及其作用机制。

slide94

名词解释:

呼吸链

氧化磷酸化。