A. Pichota et al. / Bioorg. Med. Chem. Lett. 18 (2008) 6568–6572
6571
Table 2
similar to those from other species. The substrate-binding site
can be divided into three sub main pockets, termed the S10, S20
and S30 pockets, and the metal-binding site. The S10 pocket is a
deep hydrophobic pocket, whereas the S20 and S30 pockets are shal-
low, less well-defined, solvent exposed surface depressions. The
active site of Mtb PDF is highly conserved, particularly in the S10
pocket, which is conserved across species. The nickel ion is coordi-
nated by three protein residues (His148, His152 and Cys106) and a
bidentate reverse hydroxamic acid moiety, resulting in a square
pyramidal coordination. The interactions between Mtb PDF en-
zyme and inhibitor 16a are illustrated in Figure 2; most of the
interactions are with conserved residues, and all H-bond interac-
tions are with protein backbone atoms. The crystal structure of
Mtb Ni–PDF–16a complex (Fig. 2) indicates that substituents at
P30 can be well tolerated without affecting PDF activity as their
binding site is partially solvent exposed. This finding suggests that
this position is ideally suited for the introduction of favorable phar-
macokinetic properties through various substituents. This will be
described in a separate letter.
In vitro antitubercular activity against selected strains of M. tuberculosis (MIC in
ml).
lg/
Compound
Mtb
H37Rv
INH
SM
RIF
PZA
Beijing W
MDRe
SDRa
SDRb
SDRc
SDRd
1
0.2f
0.1
0.05
0.15f
0.2
0.1
0.03
nd
0.06
nd
0.5
0.2
nd
0.5
nd
0.25
0.125
nd
0.6
nd
0.5
0.25
nd
0.25
nd
0.125
0.03
nd
0.06
nd
15a
15d
16a
16d
Gatifloxacin was used as positive control (MIC H37Rv = 0.07
l
g/ml).
a
Isoniazid single-drug-resistant (SDR) strain.
Streptomycin-resistant strain.
Rifampicin-resistant strain.
Pyrazinamide-resistant strain.
Beijing W multi-drug-resistant strain.
Average value of eight independent experiments.
b
c
d
e
f
tures contains a complex of Mtb PDF, a bound metal ion (Ni2+) and
an inhibitor. The X-ray crystal structure of 16a with Mtb PDF is
shown in Figure 2.20
In conclusion, we have identified highly potent PDF inhibitors of
Mtb and established an initial SAR. Several potent inhibitors of Mtb
PDF were identified which were also highly active against single
and multi-drug-resistant strains of Mtb, indicating their potential
use as antibacterial agents against MDR TB. The X-ray crystal struc-
ture of an Mtb PDF–inhibitor complex was solved and used to iden-
tify the structural requirements for high enzyme potency.
Based on sequence homology, PDFs are typically classified as
type I (generally from Gram-negative species) or II (generally from
Gram-positive species). Type II PDF has a larger molecular weight
than type I PDF, primarily due to sequence insertions; however,
the type I PDFs have a longer C-terminal extension than type II.
These sequence differences result in structural differences between
type I and type II PDFs.16 Amino acid sequence analysis of Mtb PDF
indicates that it has some features similar to type I PDF, such as the
extended C-terminal portion, while it also has features similar to
type II PDF, such as several insertions.21 However, the core struc-
ture of Mtb-PDF is shown to be more similar to that of a typical
type I PDF (such as Escherichia coli PDF). Similar to E. coli PDF,
Acknowledgments
The authors thank Jeasie Tan for analytical support, and Kathryn
Bracken, Neil Ryder and Beat Weidmann for helpful discussions.
Supplementary data
the structure of Mtb PDF contains three a-helices, seven b-sheets,
and three 310 helices, and all the residues from three highly con-
served motifs are structurally conserved forming the active site.
The unique feature of Mtb PDF is its unusually long C-terminal
extension, part of which forms a b-strand pairing with the b-strand
from N-terminal region. This extension has been shown to be crit-
ical for Mtb PDF activity.22 The substrate-binding site of PDF from
different bacteria species have been described previously.16
The X-ray crystal structure of Mtb PDF and bound inhibitors
were used to identify and explain the structural requirements for
the enzyme potency observed. Overall, the structures of Mtb PDF-
inhibitor complexes reveal that the active-site in Mtb PDF is very
Supplementary data associated with this article can be found, in
References and notes
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Figure 2. X-Ray crystal structure of 16a bound to Ni–PDF of M. tuberculosis. The
Ni2+ atom is colored in magenta, nitrogen atoms in blue, and oxygen atoms in red.
The compound is shown as yellow stick model in the active site. X-ray analysis
revealed that the benzoxazole part is pointing out of the active site pocket. The
critical interactions are between the chelating unit and the metal atom, the butyl
side chain (methionine mimic), and the central carbonyl atom (H-bond to V5).
Atomic coordinates have been deposited in RCSB protein data bank, with accession
code 3E3U.
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