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1:
Hemocyanin (Hc)
Exception
Notothenoids/family Channichthyidae
O2 absorbed and distributed directly by
the plasma
Can survive without O2-carrier because
of:
the high O2 content of the cold waters
of the Southern Ocean
u
Antarctic Icefish
(body temperature: -1.7oC)
Dioxygen reduction
e-
O2
e -, 2 H +
O2-
Thermodinamically unfavorable
e -, H +
e -, H +
H2O2
H2O
HO
H2O
O2-
Kinetically unfavorable
O2
unfavorable reactions
lundi 11 juillet 2011
H2O2
E = + 0.82 V
HO
H2O
Respiratory metal-containing
proteins
Hemoglobin (Hb): Fe
vertebrates (blood cells), echinoderms, annelids,
molluscs, insect larvae
Hemerythrin (Hr): Fe
marine invertebrates, annelids
Hemocyanin (Hc): Cu
molluscs and arthropods
lundi 11 juillet 2011
Dioxygen Carriers
Properties
(II)
(II)
(I)
Metaln:O2
Fe:O2
Fe2:O2
Cu2:O2
Red-purple
Colorless
Colorless
Red
Violet-pink
Blue
Metal coordination
Porphyrin ring
65
108
400 to 20 000
numb. subunits
many
Hemoglobin (Hb)
Hemoglobin is an 22 heterodimer
2
1
-chain
oxy-Hemoglobin
O
FeIII
Back
lundi 11 juillet 2011
Hemerythrin (Hr)
NHis
NHis
O
FeII
NHis
H O
O
O
NHis
FeII
O
O
O2
NHis
NHis
FeIII
FeIII
NHis
NHis
O
O
O
O
O2
deoxy-Hr
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NHis
NHis
Back
oxy-Hr
Hemocyanin (Hc)
H
N
H
N
HN
N
(I)
Cu
N
HN
H
N
(I)
O2
N
Cu
NH
HN
N
N
HN
H
N
(II)
Cu (O2) Cu
N
HN
(II)
N
HN
NH
Hemocyanin (Hc)
Hc are respiratory proteins containing 2 Cuatoms that reversibly bind a single O2.
Oxygenation causes a color change between
the colorless Cu(I) deoxygenated form and
the blue Cu(II) oxygenated form.
Hc carry O2 in the blood of most molluscs,
and some arthropods. They are second only
to Hb in biological popularity of use in O2
transport.
lundi 11 juillet 2011
Hemocyanin (Hc).
Hc is made of individual subunit proteins which contains
1 active site.
Each subunit weighs about 75 kDa. Subunits are arranged
in chains or bundles in weights exceeding 1500 kDa.
Because of the large size of Hc, it is found free-floating in
the blood, unlike Hb, which must be contained in cells
because its small size would lead it to clog and damage
blood filtering organs such as the kidneys. This freefloating nature allows for higher densities of Hc in the
blood (as compared to Hb), and helps offset its low
efficiency.
lundi 11 juillet 2011
x6
90
Oligomeric forms of Hc
6 sub-u
12 sub-u
x2
24 sub-u
x2
Hc active site
dCu-Cu = 3.8
Volbeda, A., Hol, W. G. et al. (1989) J. Mol. Biol. 209: 249-279
lundi 11 juillet 2011
H
N
H
N
HN
N
(I)
Cu
N
HN
(I)
N
Cu
NH
O2
HN
N
N
HN
H
N
(II)
(II)
Cu (O2) Cu
NH
N
HN
HN
H
O
Cu
O
Cu
O
Terminal
-1 (end-on)
H
O
Cu
O
Cu
O
Cu
Cu
O
cis--1,2
trans--1,2
-1:1 (end-on)
O
Cu
Cu
-1,1
Cu
Cu
Cu
Biomimetic/bioinspired
model
RH + O2 ROH + H2O
lundi 11 juillet 2011
meta-Xylyl ligand
Br
OH Br
N
H
OH N
N
N
Terminal peroxo
O2
N
O
Cu
Cu
CH2Cl2
184 K
Cu
k-1
EPR: Silent
k1
Cu
O O
O
Cu
O2
N
Cu I
CH2Cl2
r. t.
II
II
Cu
Cu
N
N
N
1 e- reduction
O
Cu
N
I
O2
N
II
Cu
N
CH2Cl2
r. t.
II
II
Cu
Cu
N
N
N
tris-(2-pyridylmethyl)amine (TPA)
N
(iPr)2EtNH
NH2
+
N
Br
N
NH2
R1
+
O
R2
NaBH4
R1
N
R1
N
NH
R2 (iPr)2EtNH
N
R3
R2
Br
R3
1
1
- :
peroxo (end-on)
O2
N
N
k1
N
Cu
N
N
N
N
Cu
O
k-1
EtCN or THF
183 K
N
Cu
M-1 cm-1)
EPR: Silent
EPR: Silent
lundi 11 juillet 2011
Substituted TPA
R
R
R
N
N
N
Cu
O2
k1
N
k-1
Cu
N
EtCN
183 K
R = H & MeO
N
O
N
Cu
N
R
H = -47.2/-49 kJ mol-1
S = -89/-87 J K-1 mol-1
Pyrazolylborates (scorpionates)
R
NaBH4
N NH
N
H
N
N N
B
N
anisole
R
- H2
R
K
2
2
- :
R
H
R
N N
Cu
NN
O2
k-1
EtCN or THF
183 K
k1
S
R
peroxo
H
R
N N
Cu
NN
R
O
O
R
R
N N
Cu
NN N
EPR: Silent
EPR: Silent
Structure of oxy-Hc
limulus polyphemus
O2
k1
N
N
Cu
Cu
N
k-1
CH2Cl2
184 K
Cu
Cu
O
N
N
unstable
R
H
tBu
F
NO2
k1 x 102(M-1s-1)
3.85
4.90
0.093
1.09
K x 107
2.6
9.6
0.33
0.59
N
Cu
CH2Cl2
184 K
Cu
N
Cu
Cu
O
Biomimetic
O2
N
O
Cu
Cu
N
CH2Cl2
184 K
Cu
N
Cu
O O
Bioinspired
Spacer
N
Spacer
N
Cu
O2
N
II
II
Cu
Cu
N
Cu
O2
()n N
Cu
Cu
N
O2
O Cu
Cu
O
Cu
O
H = -58 kJ mol-1
S = -165 J K-1 mol-1
k1 = 11 103 M-1s-1
K = 4.5 102
CH2Cl2
184 K
Cu
N
O2
N
N
H = -28 kJ mol-1
S = -101 J K-1 mol-1
O2
Spacer
LCu(I)
Cu(I)L
k1
Spacer
LCu(II)
k-1
O2
LCu(II)
Cu(II)L
Spacer
LCu(II)
k-1
LCu(II)
O2
Cu(II)L
O2
Spacer
Cu(II)L
O2
Cu(I)L
O2
Spacer
LCu(II)
k1
Spacer
Spacer
Cu(II)L
LCu(II)
O2
O2
LCu(II)
Cu(II)L
Spacer
Cu(II)L
O2
1,4,7-Triazacyclononane (TACN)
Ts
Ts
N
N
H
+
TsO
1) CsCO3/DMF
2) H2SO4
3) RX/NEt3
O2
N
k1
Cu
N
R
k-1
EtCN or THF
183 K
R
O
Cu
Cu
N
R
N
N
N
R
OTs
N
R
N
H
Ts
Ph
()m
N
II I
()n
Cu
CT CuIIO22O2
Absorbance
1.5
Ph
()m
d-d
0.5
N
Cu
0
389
459
529
599
669
()n
Cu
(nm)
()n
N
()m
Ph
n or m = 0 or 1
LCu(I)
O2
k1
LCu(I)
LCu(II)O2
fast
k-1
LCu(II)O2Cu(II)L
CH3
N
N
II I
Cu
H = -0.7 kJ mol-1
S = -164 J K-1 mol-1
H = -89 kJ mol-1
S = -240 J K-1 mol-1