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Na
Ca
Mg
Cl
Zn
Si
Cu
As
Mn
Mo
Se
I
Co
Br
+1
Mg2+,Ca2+
+2
Zn2+, Ni2+
+2
Stability of
complex
Very low
Low to
medium
High
High (medium
for Mn2+ and
Fe2+)
Favored
donor atoms
Oxygen
Oxygen
Sulfur or
nitrogen
Sulfur or
nitrogen
(oxygen for Mn
and Fe)
Mobility in
biological
media
Very mobile
Semi mobile
Static
Static, semi
mobile for Mn2+
and Fe2+
Glucose
Hemoglobin
Fe2+
Na+
intestine
mitochondria
O2
Glucose
H2O
liver
Mg2+
Mn2+
K+
Ca2+
PO43-
PO43Fe2+
Mg2+
Cu2+
Fu nct io n
E nz ym e C lass
M ag nesiu m
C a lc iu m
P otassiu m
k ina ses
hydro lase s
p yru vate kina se
Iro n
Z inc
C o pper
M a nga nese
C o ba lt
S e le niu m
c yto chro m es
D N A bind ing
o xida ses
o xida ses
m utases (w ith B 12)
pero xidases
Metalloenzyme
1. Metal in equilibrium
5. Electrostatic bonding
Examples of Metalloenzymes
Manganese
Arginase
Water splitting enzyme
Pyruvate carboxylase
Cobalt (with B12)
Methylmalonyl CoA mutase
Homocysteine transmethylase
Molybdenum
Nitrogenase
Xanthine oxidase
Calcium
Iron
Thermolysin
Ribonucleotide reductase
Cytochrome oxidase (with Cu)
Nickel
Urease
Lewis acid
Enzyme cofactor
Protein structure
Hormone activator
Neurotransmitter
Genetic expression regulator
Fe2+, Fe3+
Heme iron
Electron transport
Oxygen activator
Oxygen carrier
Cu+, Cu2+
Enzyme cofactor
Oxygen carrier
Oxygen activator
Iron metabolism
Se
Redox reactions
Antioxidant
Insulin mimetic
Glucose metabolism
Mo2+
Enzyme cofactor
Nitrogen activator
HPO4=, Si
Acid-base non metals
Biomineralization
Co3+
Vitamin b12
Mn2+
Enzyme cofactor (limited)
Ni2+
Coenzyme
Remnant of early life
Examples of Metalloproteins
Function
1. Metallothionein
2. Ferritin
3. Calmodulin
4. Transferrin
Iron transport
5. Selenoprotein W
Selenium transport
6. Calbindin
Calcium transport
Biomineralization
Calcium and phosphate
Bones and Teeth
Trebecular bone of
the lower spine.
Changes with
aging.
Zinc Function
300 enzymes require zinc
DNA, RNA polymerases
Metal Ions in CatalysisOne third of all enzymes require a metal ion for catalysis
Zn 2+Polarizes H2O,
making it a better
nucleophile
His
His Zn2+
His
..
O
H
His
O
+ C
O
His Zn2+
His
C
O
H2 O
His
His Zn2+
His
Displaces HCO3-
..
O
H
+ H+
+ H O
O
Bicarbonate
Biochemical Iron
Function
Oxygen Transport & Storage
Hemoglobin
Myoglobin
Ribonucleotide reductase
Amino acid oxidases
Fatty acid desaturases
Nitric oxide synthetase
Peroxidases
Transport Mechanism
A bucket-brigade
..
NADH
NAD+
..
FMN CoQH2
..
..
Cyt b Cyt c1
(Fe3+) (Fe2+)
..
Reduced
-0.32 volts
Cyt c1
(Fe3+)
Cyt
Cyt c a+a3
(Fe3+) (Fe2+)
Cyt c Cyt
(Fe2+) a+a3
.. (Fe3+)
O2
H2O
..
Oxidized
+ 0.82 volts
Dinitrogenase
A c t iv a t e d
0 .4 0
Fe
F d
-e-
F d
M o
M o -H
R
R
M o -H
0 .2 9
e-
A TP
N=N
H
H - M o -H
H
A D P
H2
Dinitrogenase Reductase
H -M o = N = N
Fd-e-
M o
R
R e-
Fd
A TP
ADP
H -M o = N -N H 2
e + H+
e+
Fd-e-
H+
Fd
NH3
R eA TP
A DP
M o = N
NH3
e+
N2 + 3H2 2NH3
H+