Figure 22-48 Schematic diagram depicting the coordinated control

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							                 Figure 22-48
                       Schematic
           diagram depicting the
           coordinated control of
              glycolysis and the
              citric acid cycle by
            ATP, ADP, AMP, Pi,
                 Ca2+, and the
            [NADH]/[NAD+] ratio
             (the vertical arrows
Page 837




            indicate increases in
                    this ratio).
Much as I hate to skip stuff in this chapter, we will cover pp 843-850 and
862-870. Please read section 3 on glycoprotein synthesis, pp 852-861.

You should be able to do all the problems…
           Gluconeogenesis

• This route is important when fasting
• Precursors: lactate, pryuvate, TCA
  intermediates, most aa’s (except leu,lys)
• Entry into gluconeogenisis: OAA
• Note that animals cannot make glucose
  from AcetylCoA (plants have the
  glyoxylate cycle)
Page 844




Figure 23-1 Pathways
converting lactate,
pyruvate, and citric acid
cycle intermediates
to oxaloacetate.
   Synthesis and degradation are
         always separated
• The really good news: Mostly glycolytic
  enzymes involved.
• What irreversible enzymes of glycolysis
  must be bypassed for
  gluconeogenesis????
• PK, PFK, HK
            Figure 23-2 Conversion of
            pyruvate to oxaloacetate and
           then to phosphoenolpyruvate.

             Prosthetic group=biotin
Page 845




                                       Hi energy intermediate
    Figure 23-3a Biotin and carboxybiotinyl–
enzyme. (a) Biotin consists of an imidazoline ring
  that is cis-fused to a tetrahydrothiophene ring
           bearing a valerate side chain.
                                            Raw eggs contain avidin—a protein with
                                            very high affinity for biotin
                                            Bacteria (Streptomyces) make avidin
                                            analogs like streptavidin—where did we
                                            see this recently???




http://www.rpi.edu/dept/bcbp/molbiochem/MBWeb/mb1/part2/chime/biotin/btn-index.html
   Figure 23-3b Biotin and carboxybiotinyl–
enzyme. (b) In carboxybiotinyl–enzyme, N1 of the
  biotin ureido group is the carboxylation site.


                            Another swinging arm between 2
                            acitive sites of enzyme!
Page 845
 Figure 23-4 Two-phase reaction
mechanism of pyruvate carboxylase.
        Phase 1: carboxylation of biotin
                Figure 23-4 (continued) Two-phase
                  reaction mechanism of pyruvate
                            carboxylase.
                             Phase II: carboxylation of pyruvate



                                                                   PEP
                                                                   nucleophillically
                                                                   attacks CO2
Page 846




                                             Biotin accepts
                                             H+ from
           CO2 produced in active            pyruvate→PEP
           site via elimination
  Pyruvate Carboxylase Facts
• Catalyzes an important anaplerotic
  reaction that increases TCA activity
• Acetyl-CoA allosterically activates PC*

•*If TCA is inhibited by hi ATP/NADH, OAA →gluconeogenesis
Figure 23-5 The PEPCK
mechanism. GTP driven
decarboxylation of OAA
→PEP
           Figure 23-6
           Transport of
           PEP and
           OAA from
           the
           mitochondria
           to the cytosol.


           2 different
           routes—
           either via
           malate or asp

              Malate
Page 847




              shuttle also
              moves
              NADH
              (required in
              cytosol for
              gluconeo-
              genesis
Glc-6-Phosphatase unique to kidney and liver
They supply other tissues with glc.




               Figure 23-7
                 Pathways of
            gluconeogenesis
             and glycolysis.
 Page 848
              Table 23-1 Regulators of
           Gluconeogenic Enzyme Activity.
Page 849
           Figure 23-9   The Cori cycle.
Page 850
            Cells’ second energy currency:
                       NADPH!
•   NADPH is required for reductive biosynthesis
     –   FA’s
     –   Steroids
     –   Photosynthesis               Most cells maintain their [NAD+]/[NADPH] near 1000!!!
     –   Etc.

•   NADPH is generated by oxidation of G6P
     – Pentose phosphate pathway (PPP) = hexose monophosphate shunt= phosphogluconate
       pathway
     – 3 G6P + 6 NADP+ + 3 H2O →6 NADPH + 6 H+ + 3 CO2 + 2 F6P = GA3P

•   Pathway divided into 3 phases
     – Oxidative Reactions
          • Produces Ribulose-5-P
     – Isomerization/Epimerization Reactions
          • Produces Ribose-5-P and Xyulose-5-P
     – Transaldolase and Transketolase Reactions
          • 3 Ru5P ↔r5P + 2 Xu5P
     Figure 23-25 The pentose phosphate pathway.
Page 863
           Figure 23-26 The glucose-6-
            phosphate dehydrogenase
                     reaction.
Page 864
             Figure 23-27 The
              phosphogluconate
           dehydrogenase reaction.
Page 864
           Figure 23-28 Ribulose-
           5-phosphate isomerase
                   and ribulose-
                   5-phosphate
                   epimerase.
Page 865
Figure 23-29
Mechanism of
transketolase.
Page 865
           Figure 23-30
           Mechanism of
           transaldolase.
Page 866
           Figure 23-31 Summary of carbon skeleton
            rearrangements in the pentose phosphate
                           pathway.
Page 867
“Alfonse, Biochemistry makes my head hurt!!”
 \
Page 844




Figure 23-1 Pathways
converting lactate,
pyruvate, and citric acid
cycle intermediates
 to oxaloacetate.
            Figure 23-2 Conversion of
            pyruvate to oxaloacetate and
           then to phosphoenolpyruvate.
Page 845
  Figure 23-3a       Biotin and carboxybiotinyl–
enzyme. (a) Biotin consists of an imidazoline ring
 that is cis-fused to a tetrahydrothiophene ring
          bearing a valerate side chain.
           Figure 23-3b Biotin and carboxybiotinyl–
           enzyme. (b) In carboxybiotinyl–enzyme, N1
                of the biotin ureido group is the
                       carboxylation site.
Page 845
              Figure 23-4 Two-phase
           reaction mechanism of pyruvate
                     carboxylase.
Page 846
           Figure 23-4 (continued) Two-phase
             reaction mechanism of pyruvate
                  carboxylase. Phase II
Page 846
Page 847




           Figure 23-5 The PEPCK
           mechanism.
           Figure 23-6
Page 847




           Transport of
           PEP and OAA
           from the
           mitochondrion
           to the cytosol.
              Figure 23-7
                Pathways of
           gluconeogenesis
            and glycolysis.
Page 848
              Table 23-1 Regulators of
           Gluconeogenic Enzyme Activity.
Page 849
     Figure 23-25 The pentose phosphate pathway.
Page 863
           Figure 23-26 The glucose-6-
            phosphate dehydrogenase
                     reaction.
Page 864
             Figure 23-27 The
              phosphogluconate
           dehydrogenase reaction.
Page 864
           Figure 23-28 Ribulose-
           5-phosphate isomerase
                   and ribulose-
                   5-phosphate
                   epimerase.
Page 865
Figure 23-29
Mechanism of
transketolase.
Page 865
           Figure 23-30
           Mechanism of
           transaldolase.
Page 866
           Figure 23-31 Summary of carbon skeleton
            rearrangements in the pentose phosphate
                           pathway.
Page 867
PPP Song
           Figure 24-1    Chloroplast from
                         corn.
Page 872
           Figure 24-3 Chlorophyll
                  structures.
Page 874
           Figure 24-3 (continued)
               Chlorophyll structures.
Page 874
Figure 24-4
Energy
diagram
indicating the
electronic
states of
chlorophyll
and their most
important
Page 875




modes of inter-
conversion.
           Figure 24-5 Absorption
              spectra of various
           photosynthetic pigments.
Page 875
Figure 24-7a Flow of energy through a
photosynthetic antenna complex. (a) The
excitation resulting from photon absorption
randomly
migrates
by exciton
transfer.
Page 877
Figure 24-7b Flow of energy through a
photosynthetic antenna complex. (b) The
excitation is trapped by the RC chlorophyll.
Page 877
   Figure 24-9 Model of the light-absorbing
antenna system of purple photosynthetic bacteria.
Page 878
           Figure 24-13a        Photosynthetic electron-
            transport system of purple photosynthetic
                bacteria. (a) A schematic diagram.
Page 883
   Figure 24-13b The approximate standard
    reduction potentials of the photosynthetic
electron-transport system’s various components.
Page 883
Page 885




           Figure 24-15     The Z-scheme
           for photosynthesis in plants
           and cyanobacteria.
           Figure 24-17 Schematic representation of
              the thylakoid membrane showing the
           components of its electron-transport chain.
Page 886
           Figure 24-18 Detailed diagram of the
                Z-scheme of photosynthesis.
Page 887
           Figure 24-22 Schematic mechanism of O2
                   generation in chloroplasts.
Page 889
           Figure 24-29 Segregation of
                  PSI and PSII.
Page 894
Figure 24-
31
The Calvin
cycle.
Page 896
Table 24-1 Standard and Physiological Free
Energy Changes for the Reactions of the Calvin
                    Cycle.
Page 901
Figure 24-32
Algal 3BPG
and RuBP
levels on
removal
of CO2.
Page 898
           Figure 24-33a        X-Ray structure of
              tobacco RuBP carboxylase. (a) The
           quaternary structure of the L8S8 protein.
Page 899
Page 900




Figure 24-34 Probable
reaction mechanism of
the carboxylation
reaction catalyzed by RuBP carboxylase.
           Figure 24-35
                   Light-
               activation
           mechanism of
              FBPase and
                 SBPase.
Page 902
           Figure 24-36 Probable mechanism of the
             oxygenase reaction catalyzed by RuBP
                   carboxylase–oxygenase.
Page 902
 Figure 24-37
Photorespiration.
Page 903
           Figure 24-38 The C4 pathway.
Page 904
           PS SONG


http://www.csulb.edu/~cohlberg/So
      ngs/photosynthesis.mp3
“Alfonse, Biochemistry makes my head hurt!!”
 \

						
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