| Research Article |
Open Access |
|
| Molecular Docking Studies of Curcumin Derivatives with
Multiple Protein Targets for Procarcinogen Activating Enzyme
Inhibition |
| C.R. Girija1*, Prashantha Karunakar1, Chetan S Poojari1, Noor Shahina Begum2 and Akheel Ahmed Syed3 |
| 1Department of Chemistry, SSMRV College, 4thT Block, Jayanagar, Bangalore-560041, India. |
| 2Department of Studies in Chemistry, Bangalore University, Central College Campus, Bangalore-560001, India. |
| 3Department of Studies in Chemistry, University of Mysore, Manasagangothri, Mysore-570006, India. |
| *Corresponding author: |
C.R. Girija, Department of Chemistry,
SSMRV College,
4th T Block, Jayanagar,
Bangalore-560041, India,
Tel: +91 98864 19952,
E-mail: girijashivakumar@rediffmail.com |
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| Received May 25, 2010; Accepted June 26, 2010; Published June 26, 2010 |
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| Citation: Girija CR, Karunakar P, Poojari CS, Begum NS, Syed AA (2010)
Molecular Docking Studies of Curcumin Derivatives with Multiple Protein Targets
for Procarcinogen Activating Enzyme Inhibition. J Proteomics Bioinform 3: 200-
203. doi:10.4172/jpb.1000140 |
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| Copyright: © 2010 Girija CR, et al. This is an open-access article distributed under
the terms of the Creative Commons Attribution License, which permits unrestricted
use, distribution, and reproduction in any medium, provided the original author and
source are credited. |
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| Abstract |
| Curcumin derivatives which are very potent antioxidant, free radical scavenger and known inhibitor of dioxygenases
have been extensively studied to explore their potential utilization in chemoprevention. The main objective of the present
work is to perform a docking analysis of curcumin derivatives: Tetrahydrocurcumin (THC), Bisdemethoxy curcumin
(BDC). Docking studies of these were performed using GOLD and AutoDock into a few well validated targets of
anticancer therapy (COX-2, PhenolsulphoTransferases, Matrix metalloproteinases (MMPs), P450 and TNF-alpha). A
good correlation was observed in binding affinity of THC and BDC against the targets indicating these derivatives are
potent procarcinogen activating enzyme inhibitors. |
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| Keywords |
| Docking; Procarcinogen inhibitors; Anticancer therapy
targets; Tetrahydrocurcumin; Bisdemethoxycurcumin |
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| Introduction |
| Curcumin [1,7-bis (4-hydroxy-3-methoxyphenyl)-1, 6-heptadiene-
3,5-Dione] is the major component of the Curcumin species used as
a yellow coloring and flavoring agent in foods. Curcumin has shown
anti-carcinogenic activity in animals as indicated by its ability to block
colon tumor initiation by azoxymethane and skin tumor promotion
induced by phorbol ester TPA. It is proposed that curcumin may
suppress tumor promotion by blocking signal transduction pathways
in the target cells (Lin and Lin-Shiau, 2001). Curcumin has been
demonstrated to have potent antioxidant (Kunchandy and Rao, 1990;
Subramanian et al., 1994; Sreejayan and Rao, 1994), anti-inflammatory
activity (Huang et al., 1988; Conney et al., 1991; Huang et al., 1997;
Liu et al., 1993), to inhibit the carcinogen-DNA adduct (Conney et
al., 1991) and tumorigenesis in several animal models (Huang et al.,
1992; Huang et al., 1994; Huang et al., 1995; Rao et al., 1995). |
As a part of our continuing program to discover procarcinogen
inhibitory compounds, curcumin derivatives were studied.
Tetrahydrocurcumin(THC) and bisdemethoxycurcumin(BDC) Figure
1, are the reduced form of curcumin, derived from curcuminoids and
can also be extracted from the roots of Curcuma longa, commonly
called turmeric root (Govindarajan, 1980). Tetrahydrocurcuminoids
are colorless unlike bisdemethoxycurcumin an yellow curcuminoid
which are used in color-free foods and cosmetic products. An
antioxidant used in a cosmetic application should have the capability
of efficiently quenching any radicals on the surface of the skin. In this
context, compound THC displays superior free-radical scavenging
ability and also exhibits antioxidant, anti-inflammatory and skinlightening
actions (Sugiyama et al., 1996; Rao et al., 1982) and
anticancer activity (Huang et al., 1995). It is thought that the p-hydroxy
functional groups in THC are responsible for the antioxidant activity
and keto groups are responsible for the chemopreventive action of
the compound (Rao et al., 1995; Halliwell and Gutteridge, 1985). The
crystal structures (Figure 2a and Figure 2b) of THC abd BDC have
been determined using X-ray crystallography and the results have
been extrapolated for docking analysis (Girija et al., 2004). |
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|
Figure 1:Structure of THC and BDC as viewed in Chem3D Ultra with atom
coloring. |
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Figure 2a: The structures of the compounds THC and BDC showing 50%
probability displacement ellipsoids and the atom numbering scheme. |
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Figure 2b:Comparison in Binding Energy of THC and BDC using AutoDock 3.0. |
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| The concept of docking is important in the study of various
properties associated with protein-ligand interactions such as binding
energy, geometry complementarity, electron distribution, hydrogen
bond donor acceptor properties, hydrophobicity and polarizability.
Since molecules in nature have a tendency to be found in their low
energy form, the final configuration should also be of low energy
(Pyne and Gayathri, 2005). Understanding these properties is crucial in rationale
design of potent inhibitors. |
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| Materials and Methods |
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| Preparation of ligand structures |
| The small-molecule topology generator Dundee PRODRG 2 server
(Schuttelkopf and van Aalten, 2004) is used for ligand optimization,
a tool for high-throughput crystallography of protein-ligand
complexes which takes input from existing coordinates or various
two-dimensional formats and automatically generates coordinates
and molecular topologies suitable for X-ray refinement of proteinligand
complexes. CambridgeSoft– ChemOffice 6.0.1(CambridgeSoft.
com, Cambridge, MA, USA) tool used for physicochemical properties
of THC and BDC (Table 1). |
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Table 1: Physicochemical properties of THC and BDC. |
|
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| Preparation of protein structures |
| Availability of several experimentally determined threedimensional
structures of COX-2 (1PXX), Phenol sulpho Transferases
(1LS6), Matrix metalloproteinases (MMPs) (1GKC), P450 (1OG5) and
TNF-alpha (1A8M) co crystallized with various inhibitors provides
an excellent basics for using structure-based approaches for the
discovery of new inhibitors. All water molecules and if present,
ligands were removed from the proteins for docking studies. |
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| Protein-ligand interaction using autodock and GOLD |
Autodock (version 3.0): AutoDock 3.0 includes Lamarckian
Genetic Algorithm search engine and an empirical free energy
function for estimating binding energy, docking energy, inhibitory
constant, intermolecular energy, torsional energy and internal energy.
Four binding energy terms were included in the score function:
electrostatic, van der wall, hydrogen bonding and desolvaion effect.
The binding free energy is empirically calculated based on these
energy terms and a set of co-efficient factors (Morris et al., 1998). |
Using MGLTools 1.5.1, a grid spacing of 0.374 Å with 60x60x60
points for all Proteins was prepared. The grid was centered around
the catalytic clef of the enzyme for docking. Docking for 100 number
of GA run was carried out using Lamarckian Genetic Algorithm (LGA)
and all other parameters set to default. The top ranked model in the
lowest energy cluster with maximum cluster size was considered for
all further interaction studies. |
GOLD (version 2.1.2): GOLD, which is available through the
Cambridge Crystallographic Data Center (CCDC) utilizes a genetic
algorithm that was originally described by Jones and colleagues
and an evolutionary strategy involving three genetic operators;
crossover, mutation and migration (Jones et al., 1997; Jones et al.,
1995). It was the first algorithm to be evaluated on a large dataset of
complexes, possesses an empirical free energy scoring function that
estimates the free energy of binding permitting inhibition constants,
Ki to be calculated. Although initial applications of GOLD and the
GA employed provided poor convergence results for hydrophobic
ligands, It has recently been validated using a test set of 305 diverse
protein-ligand complexes and 72% of the top-ranked solutions were
deemed accurate using the authors’ self-imposed stringent success
criteria (Nissink et al., 2002). |
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| Results and Discussion |
| In assessment using AutoDock 3.0, BDC showed better affinity
with all anticancer therapy targets than THC. Interaction of BDC
with respect to Matrix Mettaloprotease (MMPs) is represented. A
docking energy of -11.46 Kcal/mol with three hydrogen bonds was showed. The hydrogen bond was formed between hydroxyl (H14) of
the phenyl ring and carboxyl (O) of hydrophobic amino acid Pro421
by a distance of 2.114 Å (O-H. . . O) and energy of -0.374 Kcal/mol.
Another interaction bridging (O5) of the heptane branch and amine
(NH2) of positively charged residue Arg424 with a distance of 1.793
Å(N-H. . .O) along a minimum energy of -5.492 Kcal/mol. The hydroxyl
(H74) of another phenyl ring and carboxyl (O) of hydrophobic amino
acid Pro 430 by a distance of 1.858 Å(O-H. . .O) along with a energy
of-1.817Kcal/mol (Figure 3a). |
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|
Figure 3a: Binding mode of BDC (shown in Green Molecular Surface model) to
MMPs (Left). Binding mode of BDC in the active site (top view) of MMPs along
with interacting amino acids(Right) from their respective regions of active site. |
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Figure 3b: Comparison in Binding Energy of THC and BDC using GOLD |
|
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| From GOLD also it was observed that BDC showed better affinity
with COX-2 and Matrix Mettaloprotease (MMPs) than Phenol sulpho
transferases, P450, TNF-alpha anticancer therapy targets though THC
showed good affinity to Phenol sulpho transferases, P450 and TNFalpha
(Figure 3b). |
| |
| Conclusion |
| Analysis of these docked ligands with the proteins brought
in focus some important interactions operating at the molecular
level. The six-membered phenyl ring plays a vital role in holding
the molecule at place (binding) at the active site by three important
hydrogen bonds. The present study also attempts a 3D-QSAR
study on curcumin derivatives. Applying Lipinski’s Rule of five to
curcumin derivatives to evaluate druglikeness (absorption,distribu
tion,metabolism and excretion), there was no violation of the rule
determining drugs pharmacological activity in the body. These
studies are expected to provide useful insights into the roles of
various substitution patterns on the curcumin derivative and also
help to design more potent compounds. The docking studies and
3D-QSAR indicate that substitution of electron–rich compounds may
lead to improved biological activity of curcumin derivatives. Thus this
study will be useful for the design of novel procarcinogen activating
enzyme inhibitors based on docking methods. |
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| Acknowledgement |
| CRG and PK thank RSST and Principal SSMRV Degree College for their
encouragement and support. |
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