BIOINORGANIC CHEMISTRY A Short Course Second Edition

(lu) #1

394 IRON-CONTAINING PROTEINS AND ENZYMES


(Nε 2 – Fe = 2.03 Å ) and met160 (S δ – Fe = 2.37 Å ). The heme is covalently anchored
to the protein through aa residues cys37 and cys40. The cysteine residues occur
in a typical cytochrome c CXXCH pattern — in this case cys37 – ser38 – ser39 –
cys40 – his41. The propionate groups of heme c 1 participate in salt bridges with
arg120 of the cytochrome c 1 protein and with his161 of the Rieske iron – sulfur
protein (of the opposite monomer). The [2Fe – 2S] center of the ISP is held in
place by bonds to four ISP aa residues: his141 (Fe 2 – N δ 1 = 2.18 Å ), his161
(Fe 2 – N δ 1 = 2.17 Å ), cys139 (Fe 1 – S γ = 2.21 Å ), and cys158 (Fe 1 – S γ = 2.25 Å ).
The cytochrome b protein contains two hemes, heme b L (L = low potential,
also called b 565 in the literature) and heme b H (H = high potential, also called
b 562 in the literature). Cytochrome b is composed of eight transmembrane
helices (A to H). There are seven extra - membrane loops connecting the trans-
membrane helices. Of these, loops AB (with short helix ab), CD (featuring
short helices cd1 and cd2 and a hairpin turn) and EF (with short helix ef) pass
through the intermembrane space and are important participants in forming
the Q o cavity. This cavity extends into the membrane from the intermembrane
space, and it sits between the [2Fe – 2S] center of the ISP and heme b L. The
long DE loop is on the matrix side of cytochrome b, helping to form the bound-
ary of the Q i pocket that is located near the matrix extending upward into the
membrane. (See Figure 7.28 and Figure 1 of reference 86 .)


Figure 7.28 Secondary structure of the cytochrome bc 1 complex.

intermembrane space side

246

E

220

PEWY sequence-residues 270


  • 273 in bovine cyto b


11 a 18
N

61
ab 72

252
257

EF loop
CD loop

EF loop

AB loop 137 cd1 152

165 cd2 156

54 274 ef 283

A

28

75

B

104

DE loop

matrix side

22–24

133

CD

100

171

204

F1

F2

286

304

G

340

318

H

346

379
C

305
308

219–217

his83
heme bL
his182

heme bH
his196

his97
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