QSAR Analysis of Indole Analogues as Monoamine Oxidase Inhibitors
A. E. Medvedev, A. S. Ivanov,* A. V. Veselovsky, V. S. Skvortsov, and A. I. Archakov
Laboratory of Biogenic Amines and Laboratory “Computers in Biochemistry,”
Institute of Biomedical Chemistry, Russian Academy of Medical Sciences, Pogodinskaya Street 10,
Moscow, 119832, Russia
Received September 15, 1995
X
The quantitative structure-activity relationship (QSAR) analysis with comparative molecular field analysis
(CoMFA) of indole derivatives-monoamine oxidase (MAO) inhibitors were done. The pharmacophore
model included four features: two hydrophobic rings, one donor atom, and one acceptor site. The predictive
values (cross-validated r
2
) of QSAR analysis for the inhibition of MAO-A and MAO-B were 0.743 and
0.603, respectively. The contributions of steric and electrostatic fields in the interaction between inhibitors
and enzymes were equal. The three-dimensional arrangement of these fields for MAO-A and MAO-B
suggests that structures of active site for both enzymes are considerably differed from each other.
INTRODUCTION
Monoamine oxidase (E.C. 1.4.3.4), an integral protein of
the outer mitochondrial membrane, catalyses a reaction of
oxidative deamination of neurotransmitter monoamines in
central nervous system and peripheral tissues.
1
The enzyme
exists in two forms, MAO-A and MAO-B, initially distin-
guished by sensitivity to low concentrations of acetylenic
inhibitors, clorgyline and deprenyl, respectively. Strong
evidence now exists that these forms of MAO are different
proteins, encoded by two different genes.
1,2
In spite of essential progress in elucidation of peculiarities
of primary structure, biosynthesis of MAO and mechanisms
of its insertion into the outer mitochondrial membrane,
3,4
precise information about steric structures of substrate biding
sites of MAO-A and B is still absent. This stimulates
computer-modeling studies based on experimental data of
MAO interaction with substrates and inhibitors. One of the
first computer analysis of series of potent MAO inhibitors
revealed that common arrangement of these inhibitors
includes aromatic ring and a side chain with an amino group
located in the ring’s plane.
5
The distance between the center
of nitrogen and the ring was 0.50-0.55 nm.
6
The discovery
of MAO-mediated bioactivation of MPTP to neurotoxin
MPP
7
which causes a development of major symptoms of
parkinsonism in experimental animals gave new rise for
quantitative structure-activity relationship studies with
relevance to some structural features influencing the binding
to active sites of MAO-A and MAO-B.
8,9
Indoles are a large group of nitrogen-containing hetero-
cyclic compounds widely distributed in living world and in
its chemical environment. Some indole amines as serotonin
and tryptamine are substrates of MAO. Recently it has been
shown that isatin (2,3-dioxindole) acts as a relatively selective
inhibitor of MAO-B than MAO-A.
10
5-Hydroxyisatin ex-
hibited selective MAO-A inhibition, whilst indole and other
isatin analogues were less potent MAO-A and B inhibitors.
11
In the present report we have analyzed our experimental
data on inhibition of MAO-A and MAO-B by indole and
isatin analogues obtained in our and other laboratories.
10-13
The action of these inhibitors was readily reversible.
12
Previous pilot QSAR analysis of their inhibitory potency
revealed that molecules of selective MAO A and B inhibitors
had different sizes: 11.5 × 5.6 × 1.8 and 8.5 × 5.1 × 1.8
Å, respectively. Here we have investigated further their
quantitative structure-activity relationship (QSAR) with
molecular field analysis (CoMFA).
MATERIALS AND METHODS
Experimental data of MAO inhibitors were taken from
previous reports.
11-13
Computer Modeling. The study was carried out using
Sybyl 6.1 software (Tripos GmbH, Munich, Germany)
running on Silicon Graphics workstation Indigo-2 (R4400,
XZ). The molecular models were constructed, and their
geometry were minimized using the standard Tripos force
field. The atomic charges were calculated by Gasteiger-
Huckel method. They were used in the subsequent analysis.
PowerSearch program for Windows (Tripos GmbH, Mu-
nich, Germany) was employed for the conformation search
for flexible bonds of molecules. In our study we have used
the conformers with the lowest energy as the most probable
conformation.
The correctness of atomic charges’ distribution, calculated
by empirical Gasteiger-Huckel method, was also validated
for some molecules by quantum mechanical AM1, MNDO,
and MINDO3 methods.
14
CoMFA Analysis. The inhibitors were aligned by fitting
the indole common structure atom by atom. Initial phar-
macophore model was constructed using the DISCO pro-
gram.
15
This model was made by matching all structures of
inhibitors, with a range of tolerance from 0.5 to 5.0 by 0.5
and features requirement from 3 to 7. Then the CoMFA
analysis was carried out in QSAR option of Sybyl. The
region was generated automatically by the program. Both
steric and electrostatic fields were taken into investigations.
The steric and electrostatic potentials were generated by using
an sp
3
carbon probe and a +1 charge. QSAR analysis was
made using PLS technique in two steps. At first using 10
components and cross-validation groups equal to a number
of compounds the optimal number of components was
determined. The second step was made with the determined
optimal number of components and without cross-validation.
X
Abstract published in AdVance ACS Abstracts, June 15, 1996.
664 J. Chem. Inf. Comput. Sci. 1996, 36, 664-671
S0095-2338(95)00126-0 CCC: $12.00 © 1996 American Chemical Society
+ +