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Bioenergetics and Biochemical Reaction (化學反應 (喜歡完全氧化還原態的化合物 (化學自營得到能量的方式,…

- - - - Link Title
- - - - starch
      - glycogen
      - sucrose
        
        glucose
        
        pyruvate
        
        Acetyl CoA
- - - - mevalonate
        
        isopentenyl-pyrophosphate
        
        rubber
        
        carotenoid pigment
        
        vit-K
        
        cholesterol
        
        steroid hormone
        
        bile acid
        
        cholesteryl esters
      - fatty acids
        
        eicosanoid
        
        triacylglycerols
        
        CDP-diacylglycerol
        
        phospholipids
- - - - 活化的電子受體
        
        pyridine
        
        nucleotides
        
        flavins
        
        是比NAD更強的氧化劑
        
        NAD-NADH
        
        nicotinamide ring of NAD accepts a hydrogen ion and two electrons,which are equivalent to a hydride ion
        
        在催化作用下NADH或NADPH產生可以藉由340nm的吸光值輕鬆地被觀察到
        
        FAD-FADH2
        
        can accept two electrons
        
        take up two protons
        
        去氫酶使用NAD+或是NADP+作為輔酶有立體特異性
        
        例如
        
        NAD+
        
        異檸檬酸鹽脫氫酶
        
        對nicotinamide ring的立體專一性:A
        
        α-KG脫氫酶
        
        對nicotinamide ring的立體專一性:B
        
        蘋果酸脫氫酶
        
        對nicotinamide ring的立體專一性:A
        
        谷氨酸脫氫酶
        
        對nicotinamide ring的立體專一性::B
        
        G3P脫氫酶
        
        對nicotinamide ring的立體專一性::B
        
        乳酸脫氫酶
        
        對nicotinamide ring的立體專一性::A
        
        乙醇脫氫酶
        
        對nicotinamide ring的立體專一性::A
        
        NADP+
        
        G6P脫氫酶
        
        對nicotinamide ring的立體專一性:B
        
        谷氨酸脫氫酶
        
        對nicotinamide ring的立體專一性::B
        
        脫氫酶與NAD或是NAD+的聯繫很小，輔酶會從一個酵素擴散到另一個酵素，可作為代謝物之間的可溶電子載體
        
        flavoprotein 使用的flavin nucleotide輔酶
        
        FAD
        
        acyl-CoA脫氫酶
        
        dihydrolipoyl (二氫硫辛酸)脫氫酶
        
        succinate(琥珀酸)脫氫酶
        
        G3P脫氫酶
        
        thioredoxin還原酶
        
        FMN
        
        NADH脫氫酶(complex1)
        
        Glycolate (乙醇酸鹽)氧化酶
        
        flavin nucleotide與flavoproteins最緊密連結，甚至在某些酵素中(琥珀酸脫氫酶)是共價結合
        
        flavoprotein 的一個特色是已連結的flavin nucleotide的標準還原電動勢(E)多樣性
- - - - entropy of the universe increases,does not require the the entropy increase take place in the reacting system itself
    - - for any physical and chemical change,the total amount of energy in the universe remains constant.energy may change form/transport from one region to another；neither created or destroyed.
  - - - isomerization between enantiomers:ΔG°=0
- - - - 原子產生自由基，兩邊各一
    - - 一個原子有成對的電子
- - - - ATP to ADP ；Glutamate to enzyme-bounded glutamyl phosphate
      - add NH3 cleave Pi ；glutamine formed
  - - - 1.hydrolysis of phosphoanhydride bonds磷酸酐鍵
      - 2.relief of charge repulsion
      - 3.resonance-stabalized product
      - ATP4-+H2O->ADP2-+Pi2-+H+ ΔG'°=-30.5KJ/mol
      - high activation energy for ATP hydrolysis
        
        kinetically stable
        
        activation energy 200~400KJ/mol
        
        thermodynamically unstable
        
        phosphoryl group transfer potential=-30.5kJ/mol
        
        rapid cleavage of the phosphoanhydride bonds only by enzyme
    - - groups of phosphate
        
        high energy
        
        ΔG'°<-25KJ/mol
        
        energy rich
        
        phosphoenolpyruvate(PEP)
        
        加一水水解分裂1Pi 變Pyruvate(enol form)-tautomerization->pyruvate(keto form)
        
        PEP3-+H2O->pyruvate+Pi2- ΔG'°=-61.9KJ/mol
        
        1,3-biphosphoglycerate
        
        relief of unstable phosphoanhydride
        
        3-Phosphoglyceric acid 脫H後resonance stabalization 變3-phosphoglycerate
        
        1,3BPG4-+H2O->3-PG3-+Pi2-+H+ ΔG'°=-49.3KJ/mol
        
        phosphocreatine
        
        reservoir of phosphate groups in muscle
        
        Phosphocreatine2- hydrolysis變creatine(resonance stabilization) ΔG'°=-43.0KJ/mol
        
        肌肉中ATP維持肌肉收縮數秒其ㄊ的ATP是從磷酸肌酸來的
        
        百米衝刺時，前幾秒的ATP是從磷酸肌酸來的
        
        消耗ATP；creatine phosphate ；anaerobic metabolism；aerobic metabolism
        
        ATP消耗速率~0.5kg/min
        
        Acetyl-CoA
        
        加水水解吐出CoASH 變成Acetic acid
        
        ionization 脫H resonance stabilization
        
        Acetyl-CoA+H2O->acetate+CoA+H+ ΔG'°=-32.2KJ/mol
        
        thioester 原先的G比較高，oxygen ester (因為兩個可以共振)原先的自由能比較低，所以一樣被水解變成醋酸的時候，thioester水解會比較favorable
        
        總結
        
        1.the bond strain in reactants due to electrostatic repulsion is relieved by charge separation after hydrolysis. eg.ATP
        
        the product stabalized by ionization eg. ATP,acyl phosphate,thioester
        
        product stabilized by isomerization eg. tautomerization in phosphoenolpyruvate
        
        product stabalized by resonance . eg.Creatine from phosphocreatine；carboxylate ion from acyl phosphate or thioesters,and Pi from Pi~Xhigh-energy cpds
        
        low energy
        
        ΔG'°比較不負
        
        index
        
        energy charge
        
        ATP+ADP除以ATP+ADP+AMP
        
        一般細胞大概都在0.8~0.95
        
        phosphorylation potential
        
        depends on the concentration of Pi directly related to the free energy available from ATP
- - - - 催化氧化的叫做脫氫酶
  - - - Fe+2+Cu+2<->Fe+3+Cu+1
    - - AH2<->A+2e-+2H+
    - - two electron，NAD+