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ABSTRACT
The structure of the ferrous
nitric oxide form of native sperm whale myoglobin has been determined by X-ray crystallography to 1.7 resolution. The nitric oxide ligand
is bent with respect to the heme plane: the
Fe-N-O angle is 112. This angle is smaller than
those observed in model compounds and in
lupin leghemoglobin. The exact angle appears
to be influenced by the strength of the proximal bond and hydrogen bonding interactions
between the distal histidine and the bound
ligand. Specifically, the Ne atom of histidine64 is
located 2.8 away from the nitrogen atom of
the bound ligand, implying electrostatic stabilization of the FeNO complex. This interpretation
is supported by mutagenesis studies. When histidine64 is replaced with apolar amino acids, the
rate of nitric oxide dissociation from myoglobin
increases tenfold. Proteins 30:352356, 1998.
353
Data Collection
56,610
11,674
80.1
3.1
4.4
32.7
73.1
2.5
24.4
6.4
P21
a 5 64.45
b 5 29.44
c 5 35.33
b 5 106.3
10,947
1,094
79.9
16.2
25.2
16.6
0.005
1.593
20.837
1.421
354
Fig. 1. Stereoview of the native sperm whale nitric oxide myoglobin structure. The view,
perpendicular to the heme plane, is of the ligand bound in the active site with coordinates in black
and electron density, contoured at 1.2 sigma, in silver.
TABLE II. Selected Data from Square Planar Iron-Nitric Oxide Crystal Structures
Compound
Proximal-Fe
Fe-N
N-O
Fe-N-O
Fe out-ofheme-plane
FeII(NO)N4L
FeII(NO)TPP
2.46
2.33
2.18
n.a.
2.22
2.18 6 0.03
2.00
2.04
1.72
1.72
1.72
1.74
1.72
1.74
1.74
1.72
1.89 6 0.04
1.65
1.64
1.82
1.17
1.12
1.20, 1.26
1.11
1.14
1.14, 1.12
1.1
1.22
1.15
1.15
1.11
n.a.
144
149
143, 131
144
139
138, 142
145
147
112 6 5
174
177
125, 135
0.39
0.21
0.27
0.09
0.08
0.05
0.07
20.01
0.00 6 0.01
,0.05
0.29
n.a.
FeII(NO)TpivPP
FeII(NO)TPP(4-MePip)
FeII(NO)TPP(4-MePip) CHCl3
FeII(NO)TPP(1-MeIm)
Horse hemoglobin(NO)
Lupin leghemoglobin(NO)
Sperm whale myoglobin(NO)
FeIII(NO)TPP(OH2) ClO4
FeIII(NO)OEP ClO4
Yeast cytochrome c peroxidase(NO)
Reference
17
13
16
15
15
14
18
19
This work
19
4L, tetramethyldibenzotetraazacyclotetradecine; TPP, tetraphenylporphryin; TpivPP, tetrakis(pivalamidophenyl)porphyrin; 4MePip, 4-methylpiperidine; 1-Melm, 1-methylimidazole; OEP, octaethylporphyrin, n.a., not available.
Disorder in the nitric oxide oxygen.
Scheidt, W.R., Lee, Y.J., Hatano, K. J. Am. Chem. Soc. 106:31913198, 1984.
355
k8NO
(M21s21)
kNO
(s21)
KNO
(M21)
21 (3106)
22
43
220
150
270
57
190
1.0 (31024)
0.98
1.1
8.0
12
11
3.1
1.3
21 (31010)
22
39
28
13
25
18
150
These
356
17.
ACKNOWLEDGMENTS
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