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Summary inorganic biochemistry per enzyme (NWI-MOL105)

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Summary of all enzymes relevant to the course inorganic biochemistry. This information is not only important for this course, because knowledge of these enzymes can also be very useful for later (elective) courses in the curriculum.

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  • May 2, 2022
  • 26
  • 2020/2021
  • Summary
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Enzymes in inorganic
biochemistry
Calmodulin
A lot of the Calcium in biology à hydroxyapatite: bone, tooth.
Ca2+ mainly outside cell ß Ca2+-ATPase (Na+/Ca2+ exchange)
Ca2+ high in ER/SR, Golgi apparatus and mitochondria ß SERCA
(sarco(endo)plasmic reticulum ATP-ase)
Ca2+ intracellular second messenger à binding to calmodulin
 large flexible (irregular) coordination sphere
 coordination to seven oxygen atoms: 5 from the amino acid side
chains (including a bidentate carboxylate), one from the peptide
backbone, and one of H2O
 fast exchange rates
 short lived strong signal à Ca2+ binding to calmodulin à EF-hand
conformation to activate kinases + activation of nitric oxide synthases
 nitric oxide: cellular messenger for widening of blood vessels
NADPH H + Arg + O2 à citrulline + H2O + NO


Jack bean urease
Catalyses:




Used by plants for urea recycling à ammonia for growth, obtained from animal urea (part of nitrogen
cycle)
Reaction speed up 3 x 1015
Two Ni ions in active site
 Lewis acid à acid base catalysis
 Polarize C=O bond to make C more susceptible to nucleophilic attack by OH
 Stabilizing formed C-O-
 Electron withdrawal from H2O à makes it more like hydronium ion à water
more easily dehydrated à stronger base à faster reaction
 NH2 proton donation (more like NH3/NH4) à better leaving group
 Brings reactants closer together

,Rubisco
Mg2+ enzyme à must important enzyme in nature
Mg2+
 smallest of all bulk biological elements
 Octahedral coordination geometry
 Coordinates to H2O
 Coordinated to ATP, DNA, RNA à counter ion for
charge stabilization
 Lewis acid in enzymes: stabilizes (formed) enols
and enolates ß electron withdrawal
 Less polarizing (electron withdrawing) than Zn 2+
Catalyses part of the carbon cycle
 Fixation of CO2 in Calvin cycle (photosynthesis dark reaction)
 Ribulose 1,5-bisphosphate carboxylase/oxygenase




Oxygen + ribulose-1,5-bisphosphate  phosphoglycerate + 2-phosphoglycol

Carbonic anhydrase
Zn2+ enzyme
 Zn borderline
 High in Irving Williams
 Structural role: Zn fingers, biomineralization
 Catalytic role: acid base catalysis à lewis acid
 Neutral ligand coordination to Zn2+ promotes dissociation of one H from
coordinated water
 Zn carbonyl mechanism (increasing susceptibility for nucleophilic attack
by enol stabilization/carbonyl polarization)
 Zn hydroxide mechanism (activation water to OH as nucleophile)
Present in blood circulation system
à avoids formation of gas bubbles
 Facilitates reversable dissolution of CO2 as HCO3-

Catalyses reversibly:
CO2 + H2O à HCO3- + H+
 In lungs: diffusion of CO2 to the air + lower pH à reaction balance shifts to left side
 In tissues à respiration à CO2 formation à reaction balance shifts to the right side

, Supplies CO2 to photosynthetic organisms to compensate for poor rubisco efficiency
Alpha CA: animals, Beta CA: plants, Gamma CA: bacteria à unrelated but Zn
Cd variant in marine phytoplankton




via

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