-------- Basic Metabolism --------



- - - Principles - - -


dynamic equilibrium;

enzyme reaction diagram;
 
exergon, endergon; reversible, irreversible;

Some definitions of life: 

    
                    a process far away from thermodynamic equilibrium [Eigen]

                    reproduction, metabolism and evolution  [one possibility]

                    life is a daring adventure - or nothing    [Helen Keller]

- - - a) Carbohydrates - - -



Glycolysis


glucose                      enz-glyc1: hexokinase, glucokinase  
glucose-6-phosphate enz-glyc2: phospho-gluco-isomerase
fructose-6-phosphate enz-glyc3: 6-phospho-fructo-kinase pfkA pfkB
fructose-1,6-biphosphate enz-glyc4: fructose-bi-phosphate aldolase
dihydroxyacetone-phosphate + glycerinaldehyd-3-phosphate enz-glyc5: glyceryladehyd-3-phosphate DH
1,3-bi-phospho-glycerate enz-glyc6: 3-phospho-glycerate-kinase
3-phospho-glycerate enz-glyc7: phospho-glycerate-mutase
2-phospho-glycerate enz-glyc8: enolase
phospho-enol-pyruvat enz-glyc9: pyruvat-kinase (other direction: phospho-enol-pyruvate-synthase)
pyruvate end-glyc

Entner-Doudoroff


6-phospho-gluconate          enz-EntD1: phospho-gluconate-dehydratase 
2-dehydro-3-deoxy enz-EntD2: 2-dehydro-3-deoxy 6-phospho-gluconate gluconate aldoalse
pyruvate + glyceraldehyde-3-phosphate end-EntD There are additions branching off !

Pentose phosphate cycle


glucose-6-phosphate          enz-Pent1: glucose-6-phosphate DH 
6-phospho-1,5-gluconolactone enz-Pent2: 6-phospho-gluconolactonase
6-phospho-gluconate enz-Pent3: phospho-gluconate DH
ribulose-5-phosphate enz-Pent4: ribose-phosphate-isomerase xylulose-5-phosphate + ribose-5-phosphate enz-Pent5: Transketolase seduheptulose-7-phosphate + glyceraldehyd-3-phosphate
glyceraldehyd-3-phosphate + fructose-6-phosphate enz-Pent5: Transketolase erythrose-4-phosphate + xylulose-5-phosphate
erythrose-4-phosphate fructose-6-phosphate + enz-Pent6: Transaldolase seduheptulose-7-phosphate + glyceraldehyd-3-phosphate
Note different elementary modes for pentosephosphate cycle

Citric acid cycle


synonym: TCA (tricarboxylic acid) cycle 
oxalacetate + enz-Citr1: citrate synthase Acetyl-CoA
citrate enz-Citr2: aconitase
isocitrate enz-Citr3: isocitrate DH +CO2
2-ketoglutarate enz-Citr4: 2-ketoglutarate DH +CO2
succinyl-CoA enz-Citr5: succinate-thiokinase
succinat enz-Citr6: succinat DH
fumarate enz-Citr7: fumarase
malate enz-Citr8: malate DH
oxalacetate end-Citr

polysaccharids


cellulose gluc b(1-4)         
glycogen  gluc a(1-4) and a(1-6) (branching every 30th or so)

Note: Regulation of glycogen synthesis
starch
     amylose gluc a(1-4) CHK
     amylopectin gluc a(1-4) and a(1-6) CHK

- - - b) Amino Acids - - -



ammonia assimilation



glutamate +NH3 +ATP          enz-AA1  : glutamine synthetase         glnA 
glutamine +ADP

glutamine +NADPH
+ alpha-ketoglutarate enz-AA2 : glutamate synthetase gltBD
2 glutamate + NADP

NH3 + alpha-ketoglutarate + NADPH enz-AA3 : glutamate dehydrogenase gdhA
glutamate + NADP

further nitrogen metabolizing



oxalacetate + glutamate enz-AA4 : aspartate transaminase aspC, tyrB
alpha-ketoglutarate
+ aspartate

aspartate + glutamine + ATP enz-AA5 : glu-dependent asparagine asnB
asparagine + glutamate + ADP synthetase

aspartate + NH3 + ATP enz-AA6 : ammonia dependent asparagine asnA
asparagine + ADP synthetase

pyruvate + glutamate enz-AA7 : glutamic-pyruvic alaB?
L-alanine transaminase
+ alpha-keto-glutarate

valine + pyruvat enz-AA8 : alanin-valine transaminase avtA
+ alpha-ketoisovalerate
+ L-alanine
L-alanine to D-alanine enz-AA9 : alanine racemase alr
L-alanine to D-alanine enz-AA0 : alanine racemase dadX, dadB

urea cycle


arginine
          - urea             enz : 
ornithine
          + carbamoyl-P      enz :
citrullin
          + asparagin        enz :
argininosuccinat
          - fumarat          enz :
arginine 



Common aromatic amino acid pathway


phosphoenolpyruvate +        enz-Arom1: 3-deoxy-D-arbino-heptulosonate- 
erythrose 4-phosphate 7-phosphate-synthase aroF,G,H
3-deoxy-D-arabino-heptuloso-
nate-7-phosphate enz-Arom2: 3-Dehydroquinate synthase aroB
3-Dehydroquinate
- H20 enz-Arom3: 3-Dehydroquinate dehydratase aroD
3-dehydroshikimate +NADPH,H+ enz-Arom4: Shikimate dehydrogenase
Shikimate + NADP enz-Arom5: Shikimate kinase I,II aroE
Shikimate 3-phosphate+PEP enz-Arom6: 5-Enolpyruvoylshikimate- aroK,L
5-Enolpyruvoylshikimate- 3-phosphate synthase aroA
3-phosphate enz-Arom7: Chorismate synthase aroC
Chorismate + P end-Arom

Phenylalanine biosynthesis


Chorismate                   enz-Phe1 : Chorismate mutase            pheA  
Prephenate enz-Phe2 : Prephanate dehydratase pheA
- CO2 - H2O
Phenylpyruvate enz-Phe3 : Tyrosine aminotransferase tyrB
+ Glu
Phenylalanine
+ alpha-Ketoglutarate

Tyrosine biosynthesis


Prephenate                   enz-Tyr1 : Prephenate dehydrogenase     tyrA  
4-Hydroxyphenylpyruvate enz-Phe3 : Tyrosine aminotransferase tyrB
+ Glu
Tyrosine
+ alpha-Ketoglutarate in man CHK: phenylalanine enz-Tyr2 : Phenylalaninehydroxylase tyrosine lack of it Phenylketonuria; toxic phenyl-acetic acid ?

Tryptophan biosynthesis


Chorismate   + Glutamine     enz-Trp1 : Anthranilate synthase        trpE  
Glutamate +
Anthralinate enz-Trp2 : Anthranilate phosphoribosyl
+ phosphoribosyl transferase trpD
pyrophosphate
Phosphoribosyl enz-Trp3 : Phosphoribosyanthranlinate trpC
anthranlinate isomerase
1-(o-carboxyphenylamino)-1-
deoxyribulose-5-phosphate enz-Trp4 : Indoleglycerol phosphate trpC
- CO2 synthetase
Indoleglycerol phosphate enz-Trp5 : Tryptophan synthase trpA,B
+ Serine
Tryptophan
+ glyceraldehyd
3-phosphate
 

- - - c) Lipids - - -


carriers


carnithin-cycle (carnithin amphoter, derived from lysine)x:  

acyl-CoA (cytosol)
acyl-carnithin (mitochondrial membrane)
acyl-CoA (mitochondrial matrix)

fatty acid synthesis



- unsaturated fatty acids:


ketone bodies


acetoacetate
3-hydroxy-butyrate CHK

Note: Condition e.g. in diabetes

fatty acid oxidation



- - - d) Nucleotide metabolism - - -


pyrimidine synthesis


OTP
UTP
TTP

purine synthesis


ITP
ATP
GTP

- - - e) Other - - -


Vitamins


watersoluble: 

B1, B2, B6, B12, Ascorbic acid

lipohilic:

A
D  hydroxycholecalciferol, UV, activated
E
K  gamma carboxylation of glutamic acid, important in blood clotting
   factors


-------- Higher level regulation --------



- - - a) in a cell - - -


DNA synthesis


DNA polymerase III (main enzyme in eucaryotes CHK) Note: 3'-5' exonuclease activity CHK Toxins: Cytostasis; DNA gyrase inhibitor

Transcription


RNA polymerase II

Translation




Seondary messengers



cAMP




Regulatory structures in DNA



DNA types: A,B,Z

procaryotes:
operons
regulons

eucaryotes:
histones CHK
nucleosomes
enhancers
hox genes

cell division control:

-cell cycle genes:  
                   cdc 2

-apoptosis genes:
                   p53

Regulatory RNA and higher RNA metabolism



mRNA, tRNA, rRNA; cyoplasmic RNAs: 7SL RNA, 7K RNA; viral RNA;
nuclear RNAs: snRNAs, snoRNAs;
splicing variants: self splicing introns (type I, type II)
ATAC introns;

regulatory elements: 

- in mRNA: IREs, se-cys-RNAs, 

catalytic RNAs:
hammerheads
ribozymes
RNAse P
telomerase


Lipoproteins


Chylomicrones: Resorption of fatty acids in illeum; rich in cholesterol;
IDL          : Intermediate density lipids in the liver;
VLDL         : Very low density lipids, transport to adipose tissues
LDL          : Low density lipids, transport from the adipose tissue
               into the periphery (lipids, cholesterol)
HDL          : Heavy density lipids: scavengers of cholesterol from tissue 
               degradation protective;
               enzyme: Aryltransferase CHK
enz: Lipase

- - - b) Global metabolic changes in yeast - - -



Diauxic shift (from glucose rich to glucose poor)


look at
Brown lab(Stanford) for more results on this. 710 mRNAs increased more than 2x, 183 mRNAs more than 4x 1030 mRNAs decreased more than 2x, 203 mRNAs more than 4x Gene families (well known): + aerobic ethanol utilization (aldehyd-DH, alcohol-DH, citric acid cycle, pyruvate carboxylase, glyoxylate cycle, cytochromes) + mitochondrial ribosomal genes (for mitochondria growth) + carbohydrate storage (gycogen, trehalose) + gluconeogenesis - pyruvate decarboxylase, glycolysis - protein synthesis (ribosomal proteins, tRNA synthetase, translation, elongation, intiation) Gene families (before not considered in the diauxic shift): + (late but strong, 9x induction): Glucose repressed genes with CSRE-sites as common activator for transcription + genes with STRE-sites as common activator for transcription (e.g. one putative glutathione peroxidase, a putative transaldolase) + genes with Hap2,3,4 transcription factor binding site (cytochrome c related genes, Hap4 itself is 9x induced) - 7 ribosomal proteins regulated by upstream activating sequence, recognized by transcription factor RAP1 (which is 4,4x repressed) + Only other transcription factor gene more than 3x induced (of a total of 149 factors measured here): SIP4 (interacts with Snf1, a master regulator of glucose repression) ------------------------------------------------------------------------------ DH indicates dehydrogenase; CSRE carbon source response element; STRE stress response element (sequence CCCCT); HAP (a heterotrimeric transcription activator complex, binding site CCAAT);

Effect of a transcription factor on the complete genome:


Tup1 deletion: 
+ 34 genes involved in glucose utilization and also induced by the 
     diauxic shift (e.g. Suc2, hexose transporters)
+ a-glucosidases, mating-type specific genes MFA1,MFA2; 
  DNA damage inducible RNR2, RNR4; 
  genes involved in floculation (6 from 13 have TUP1 binding site),
   cell wall mannoproteins;

Yap1 overexpression:
+ 17 genes more than 3x (5 are aryl-acohol-dehydrogenease 
- sugar permeases
_________________________________________________________________
tup1 (co-repressor with Mig1); SUC2 gene for invertase; 




- - - c) In tissues and organs - - -


Blood:



Antibody production



Complement Cascade


see cartoon
Complement system and regulators


antigen-antibody complex ->

-> several Fc fragments as part of a multivalent 
   antibody-antigen complex
   find the C1q tips

-> activating of zymogen C1r ->
   activating of zymogen C1s

-> C4 -> C2 -> C3 -> C5

->C5b forms complex with C6, C7 and C8, penetrating
the antigen carrying membrane

-> about 16 molecules C9 dock to this
   lysis of the alien cell


Blood clotting


Blood clotting cascade 

see cartoon 
Blood coagulation and fibrinolysis


Hemoglobine


cooperative or Bohr effect

see porphyrine synthesis
see iron metabolism
globin synthesis


regulation of glycogen storage


independent activating and de-activating cascade
of kinases;




Regulation of levels of lipoproteins 



Aging


cellular programs:
- four genetic complementation groups for first cell division stop signal.
- second, more final stop by telomer chopping;

aging by random processes:
- free radical attack
    see redox protection
    see glutathion reductase / peroxidase
    see catalase / superoxid dismutase
- aging of DNA / repair of DNA
    enzymes: helicase involved in Werner's syndrom

Death: thermodynamic equilibrium is close (compare with start)