PVC-supported ethylenediamine-copper(II) complex: a heterogeneous, efficient, and eco-friendly catalyst for multi-component synthesis of 1,2,3-triazoles by reaction of propargyl bromide, aromatic azides, and amines in water

Article abstract of DOI:10.1007/s11164-017-3247-2

The PVC-supported ethylenediamine-copper(II) complex (PVC–EDA–Cu⁺²) has provided a highly efficient, active, and reusable heterogeneous catalyst for click chemistry. In this work, the PVC–EDA–Cu⁺² catalyst is readily prepared by the

Full text of DOI:10.1007/s11164-017-3247-2

Res Chem Intermed
https://doi.org/10.1007/s11164-017-3247-2
PVC‑supported ethylenediamine‑copper(II) complex:
a heterogeneous, efcient, and eco‑friendly catalyst
for multi‑component synthesis of 1,2,3‑triazoles
by reaction of propargyl bromide, aromatic azides,
and amines in water
Ali Keivanloo1 · Mohammad Bakherad1 · Mina Khosrojerdi1 ·
Amir Hossein Amin1
Received: 24 July 2017 / Accepted: 29 December 2017
© Springer Science+Business Media B.V., part of Springer Nature 2018
Abstract The PVC-supported ethylenediamine-copper(II) complex (PVC–EDA–
Cu+2) has provided a highly efcient, active, and reusable heterogeneous catalyst
for click chemistry. In this work, the PVC–EDA–Cu+2 catalyst is readily prepared
by the reaction of PVC, ethylenediamine, and CuCl2·2H2O in water. The structure of
the catalyst is then characterized via diferent analytical tools. This catalytic system
shows a high activity in the multi-component synthesis of 1,4-disubstituted 1,2,3-tri-
azoles by the click reaction of propargyl bromide, aromatic azides, and amines at
room temperature. The advantages of this method are high reaction yield, short reac-
tion time, and capability of recovering and reusing the catalyst. In addition, water,
as a green medium, is used not only in the synthesis of 1,2,3-triazoles but also in
the preparation of the catalyst. A number of new 1,2,3-triazole derivatives are also
screened against two Gram-positive and Gram-negative bacterial strains.
Electronic supplementary material The online version of this article (https://doi.org/10.1007/
s11164-017-3247-2) contains supplementary material, which is available to authorized users.
*
Ali Keivanloo
akeivanloo@yahoo.com; keivanloo@shahroodut.ac.ir
1
Department of Chemistry, Shahrood University of Technology, 36199-95161 Shahrood, Iran
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A. Keivanloo et al.
Graphical Abstract
Keywords PVC · Ethylenediamine 1,2,3-triazole · Multi-component reaction ·
Propargyl bromide · Aromatic azide
Introduction
The concept of “click chemistry” refers to a type of reaction that is fast, easy to use,
versatile, wide in scope, modular, and stereospecifc. It generates little by-product
that can be removed without chromatography. In addition, the reaction proceeds
under green conditions using readily available and inexpensive starting materials
[1]. The copper-catalyzed azide–alkyne cycloaddition reaction is broadly known
as the azide/alkyne “click” reaction [2]. A signifcant copper-catalyzed reaction is
1,3-dipolar cycloaddition, in which organic azides and terminal alkynes exclusively
aford 1,4-disubstituted 1,2,3-triazoles in a regioselective manner [3–6].
1,2,3-Triazoles are an important class of organic compounds. They have enor-
mous applications in various research felds such as synthetic organic chemistry
[7–9] and material chemistry [10–12], and have biological activities [13, 14] such
as the anticancer, anti-infammatory, antitubercular, anti-allergic, antibacterial, and
anti-HIV properties [15, 16].
Among the transition metal complexes, copper(II) complexes have been known as
efcient catalysts in a variety of chemical reactions due to their being relatively inex-
pensive, having high selectivity, and use in numerous industrial applications [17–19].
Also, copper(I)-catalyzed azide/alkyne cycloaddition reactions have been developed
for the regioselective synthesis of 1,2,3-triazoles [20–26]. Simple Cu(I) salts such as
CuI, CuBr, and CuOTF are directly used in these cycloaddition reactions. Due to the
instability of Cu(I) species, these active species can be generated in situ by the reduc-
tion of the Cu(II) salts such as CuBr2, CuSO4, and Cu(OTf)2 by sodium ascorbate
[27]. This method is extremely efcient, although it sufers from some serious trou-
bles including the toxic efects of copper impurities on biological systems [28] and
copper contamination of the desired isolated products. Heterogeneous catalysts have
recently attracted considerable attention due to advantages such as lrger surface area
1 3

PVC-supported ethylenediamine-copper(II) complex: a…
(resulting in higher loading of the active sites), easy recovery and reusability, low cost,
and operational simplicity [29, 30]. Heterogeneous copper-based catalysts have been
used efectively for the synthesis of 1,2,3-triazoles. Some examples of copper spe-
cies immobilized on various supports such as zeolites [31], polymers [32], silica [33],
activated charcoal [34], alumina [35], and titanium dioxide [36] have been reported.
However, immobilization of Cu(I) salts on supports mostly sufers from the inherent
thermodynamic instability of Cu(I) ions, which results in their easy oxidation to Cu(II)
ions and/or disproportionation to Cu(0) and Cu(II). Moreover, the use of copper(I)
iodide has been avoided in many cases to prevent the homocoupling oxidative reaction
of acetylenes (Glaser-type reaction) [37, 38]. The by-products of this reaction are usu-
ally difcult to be separated from the desired products, and copper acetylide formed is
a potentially explosive reagent. To overcome the above-mentioned problems, and as
a consequence of our eforts in the development of efcient new catalytic systems for
useful synthetic organic transformations [39–42], we wish to report here an efcient
three-component synthesis of 1,2,3-triazoles in the presence of the ethylenediamine
copper(II) complex on PVC as a novel heterogeneous catalyst.
Experimental
General
All the reagents used were supplied from Sigma, Aldrich, and Merck. IR spectra
were obtained as potassium bromide pellets in the range of 400–4000 cm−1 on a
Shimadzu Model 470 spectrometer. FT-IR spectra were obtained on a Bomem MB
1
series spectrometer. NMR spectra were recorded on Bruker 300 MHz H NMR
and 75 MHz 13C NMR spectrometers. Elemental analyses were performed using
a Thermo Finnigan Flash EA micro-analyzer. Metal analyses were performed by
inductively coupled plasma–atomic emission spectrometry (ICP-AES). Morphol-
ogy of the catalyst was determined using a Hitachi (Japan) model s4160 scanning
electron microscopy (SEM) at an accelerating voltage of 15 kV. Mass spectra were
recorded on a 5975C spectrometer, manufactured by Agilent.
Synthesis of PVC–EDA
PVC (1 g) and ethylenediamine (0.6 mol) were added to a 50‐mL round‐bottomed
fask equipped with a magnetic stirrer containing H2O (20 mL). The reaction mix-
ture was stirred for 24 h at 80 °C. The resulting precipitate was fltered, washed thor-
oughly (in turn) with H2O and EtOH, and then dried.
Synthesis of PVC–EDA–Cu2+
A mixture of PVC–EDA (1 g) and CuCl2·5H2O (0.002 mol) in water (20 mL) was
stirred for 12 h at 80 °C. The reaction mixture was fltered, and the resulting precipi-
tate was washed thoroughly (in turn) with H2O and EtOH, and then dried.
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A. Keivanloo et al.
General procedure for synthesis of 1,4‑disubstituted 1,2,3‑triazoles
A mixture of an amine (1 mmol), propargyl bromide (1 mmol), and K2CO3
(2 mmol) in H2O (4 mL) was stirred at room temperature for 15 min. After con-
suming the starting materials (monitored by TLC), an aromatic azide (1 mmol),
PVC–EDA–Cu+2 (0.1 g), and sodium ascorbate (10 mol%) were added to the reac-
tion mixture. Upon completion of the reaction (monitored by TLC), the precipitate
formed was fltered, washed thoroughly with H2O, dried, and completely extracted
with hot EtOH. The solvent was evaporated, and the crude product obtained was
crystalized in a mixture of EtOH and H2O.
4‑((1‑(3‑nitrophenyl)‑1H‑1,2,3‑triazol‑4‑yl)methyl)morpholine (4c)
1
Mp, 119–121 °C; H NMR (300 MHz, CDCl3): δ = 2.55–2.60 (m, 4H, 2CH2),
3.70–3.75 (m, 4H, 2CH2O), 3.78 (s, 2H, CH2N), 7.76 (t, J = 8.1 Hz, 1H. ArH),
8.11 (s, 1H, CH of triazole), 8.20 (dd, J = 8.1, 1.2 Hz, 1H, ArH), 8.29 (dd, J = 8.1,
1.2 Hz, 1H, ArH), 8.60 (t, J = 2.1 Hz, 1H. ArH) ppm; 13C NMR (75 MHz, CDCl3):
δ = 53.5, 53.6, 66.8, 115.1, 120.8, 123.1, 125.9, 131.0, 137.8, 145.9, 148.9 ppm; IR
(KBr): ̃ꢀ = 3150, 2950, 2800, 1620, 1520 (NO2), 1445, 1345 (NO2) cm−1; ESI–MS:
m/z 289 (M+).
N‑((1‑(p‑tolyl)‑1H‑1,2,3‑triazol‑4‑yl)methyl)aniline (4f)
Mp, 160–162 °C; 1H NMR (300 MHz, CDCl3): δ = 2.32 (s, 3H, CH3), 4.23 (br., 1H,
NH), 6.69 (d, J = 8.1 Hz, 2H. ArH), 6.74 (d, J = 7.2, 1H, ArH), 7.18 (t, J = 7.8 Hz,
2H, ArH), 7.27 (d, J = 8.1 Hz, 2H. ArH), 7.45 (d, J = 8.1 Hz, 2H, ArH), 7.83
(s, 1H, CH of triazole) ppm; 13C NMR (75 MHz, CDCl3): δ = 21.1, 40.0, 113.2,
113.7, 118.1, 120.0, 120.5, 139.3, 129.5, 130.2, 134.8, 138.9, 147.6 ppm; IR (KBr):
̃ꢀ = 3400 (NH), 3150, 2900, 1600, 1460 cm−1; ESI–MS: m/z 264 (M+).
N‑((1‑(3‑chlorophenyl)‑1H‑1,2,3‑triazol‑4‑yl)methyl)aniline (4g)
Mp, 139–141 °C; 1H NMR (300 MHz, CDCl3): δ = 4.23 (br, 1H, NH), 4.59 (s, 2H,
CH2), 6.73 (d, J = 8.1 Hz, 2H. ArH), 6.79 (d, J = 7.2, 1H, ArH), 7.24 (t, J = 7.6 Hz,
2H, ArH), 7.40–7.50 (m, 2H, ArH), 7.63 (d, J = 7.6 Hz, 1H, ArH), 7.78 (s, 1H,
ArH), 7.90 (s, 1H, CH of triazole) ppm; 13C NMR (75 MHz, CDCl3): δ = 40.0,
113.2, 118.3, 118.5, 119.7, 120.7, 128.8, 129.4, 130.8, 135.6, 137.9, 147.4 ppm; IR
(KBr): ̃ꢀ = 3300 (NH), 3100, 2950, 1600, 1480 cm−1; ESI–MS: m/z 284 (M+).
1‑((1‑(4‑nitrophenyl)‑1H‑1,2,3‑triazol‑4‑yl)methyl)piperidine (4h)
1
Mp, 115–117 °C; H NMR (300 MHz, CDCl3): δ = 1.40–1.48 (m, 2H, CH2),
1.52–1.63 (m, 4H, 2CH2), 2.45–2.55 (m, 4H, 2CH2N), 7.95 (d, J = 8.8 Hz, 2H,
ArH), 8.05 (s, 1H, CH of triazole), 8.39 (d, J = 8.8, 1.2 Hz, 2H, ArH) ppm; 13C
NMR (75 MHz, CDCl3): δ = 24.1, 25.9, 54.0, 54.5, 120.3, 120.6, 125.5, 141.3,
1 3

PVC-supported ethylenediamine-copper(II) complex: a…
146.8, 147.1 ppm; IR (KBr): ̃ꢀ = 3150, 2950, 2750, 1600, 1520 (NO2), 1460, 1340
(NO2) cm−1; ESI–MS: m/z 287 (M+).
1‑((1‑(3‑chlorophenyl)‑1H‑1,2,3‑triazol‑4‑yl)methyl)piperidine (4 j)
Mp, 77–80 °C; 1H NMR (300 MHz, CDCl3): δ = 1.42–1.50 (m, 2H, CH2),
1.562–1.65 (m, 4H, 2CH2), 2.45–2.55 (m, 4H, 2CH2N), 7.38–7.43 (m, 1H, ArH),
7.47 (t, J = 7.8, 1H, ArH), 7.63–7.69 (m, 1H, ArH), 7.79–7.82 (m, 1H, ArH), 7.95
(s, 1H, CH of triazole) ppm; 13C NMR (75 MHz, CDCl3): δ = 24.1, 25.9, 54.1, 54.4,
118.3, 120.7, 128.6, 130.8, 135.5, 138.0, 146.14 ppm; IR (KBr): ̃ꢀ = 3150, 2950,
2750, 1600, 1460 cm−1; ESI–MS: m/z 276 (M+).
Antibacterial assay
The antibacterial activity of the 1,4-disubstituted 1,2,3-triazoles 4a, 4d, 4e, 4f, 4h,
and 4i were evaluated using the well-difusion method. First, the nutrient agar and
nutrient broth cultures were prepared according to the manufacturer’s instructions,
◦
and incubated at 37 C. After incubation for an appropriate amount of time, a sus-
pension of 30 μL of each bacterium was added to each nutrient agar plate. Cups
(5 mm in diameter) were cut in the agar using a sterilized glass tube. Each well
received 30 μL of a test compound at a concentration of 1000 μg/mL in DMSO.
Then, the plates were incubated at 37 °C for 24 h, after which time, the inhibition
zone was measured; the values were expressed in millimeters (mm). The antibacte-
rial activity of each 1,2,3-triazole was compared with tetracycline as the standard
drug. DMSO was used as the negative control.
Results and discussion
The use of an amine-modifed organic polymer catalyst for organic synthesis has
been recently reported [43–45]. The reaction of PVC with ethylenediamine as sol-
vent or in organic solvents at elevated temperatures or prolonged reaction times
aforded reddish-brown crosslink polymers [46–49]. However, PVC-supported eth-
ylenediamine ligands have recently been prepared under the above-mentioned con-
dition; surprisingly, this has been reported without cross-linking formation [44].
In this work, we prepared PVC-supported ethylenediamine ligands without cross-
linking as a light-yellow powder in water. This amine-functionalized PVC was sub-
sequently reacted with copper(II) chloride dihydrate in water, afording the PVC-
supported ethylenediamine-copper(II) complex. This heterogeneous and reusable
catalyst was successfully employed for the synthesis of 1,4-disubstituted 1,2,3-tria-
zoles from the reaction of propargyl bromide, aromatic azides, and amines in water
(Scheme 1).
The catalyst was prepared by a simple procedure from commercially available
starting materials. The synthesis of the PVC-supported ethylenediamine-copper(II)
(PVC‐EDA‐Cu+2) catalyst is shown in Scheme 2.
1 3

A. Keivanloo et al.
Scheme 1 Synthesis of 1,4-disubstituted 1,2,3-triazoles by reaction of propargyl bromides, amines, and
aromatic azides in the presence of a PVC-supported ethylenediamine-copper(II) complex
Scheme 2 Synthesis of PVC-supported ethylenediamine copper(II) complex from PVC, ethylenedi-
amine, and CuCl2·2H2O
PVC was functionalized by molecules to give a polymer carrying an ethylenedi-
amine ligand (PVC-EDA). The reaction was performed using PVC and an excess
amount of ethylenediamine in water. The subsequent reaction of this functionalized
polymer with copper(II) chloride dihydrate in water aforded the PVC‐EDA‐Cu+2
complex as a novel catalyst for the synthesis of 1,2,3-triazoles. To verify the for-
mation of the functionalized polymer and its corresponding Cu(II) complex, FT-IR
spectra were recorded separately at each preparation stage. The C–H vibrational
stretching bands of PVC were observed at 2974 and 2912 cm−1 (Fig. 1).
In the functionalized polymer, the NH and NH2 stretching and bending vibra-
tion bands of the immobilized ligand were observed at 3313, 3425, and 1550 cm−1.
1 3

PVC-supported ethylenediamine-copper(II) complex: a…
Complexation of the copper(II) ions with polymer-supported ethylenediamine, dem-
onstrated by the creation of an additional band at 520 cm−1, was characterized by
the stretching vibration of the Cu–N bond. In addition, the NH and NH2 stretching
vibrations of the immobilized ligands shifted to 3367 and 3436 cm−1, respectively.
These shifts to higher frequencies in the polymer-supported copper complex suggest
the coordination of the ligands to the metal ions. Scanning electron micrographs
were recorded for a single bead of pure PVC and the polymer-anchored complex in
order to observe the morphological changes. As expected, the pure PVC bead had a
smooth and fat surface, while the anchored complex showed roughening of the top
layer (Fig. 2).
Furthermore, successful functionalization of the polymer was confrmed by ele-
mental analysis. According to the results obtained, the N content of the polymer was
found to be 5.29% (1.88 mmol ligand/g), which indicated that only 11.8% of total
Fig. 1 FT-IR spectra for PVC
(a), PVC–EDA (b), and PVC–
EDA–Cu2+ (c)
1 3

A. Keivanloo et al.
chlorine was substituted by amine. The metal loading of the polymer-supported cop-
per complex, determined using ICP‐AES, was found to be 1.69% (0.25 mmol/g).
After the synthesis and characterization of the catalyst, the catalytic activity of
the PVC–EDA–Cu+2 complex in the click reaction was studied. To optimize the
reaction conditions for the synthesis of 1,2,3-triazoles, the reaction of propargyl bro-
mide, morpholine, and 3-nitrobenzene azide was used as a model reaction to study
the efects of various parameters on the reaction (Table 1). When the reaction was
performed with propargyl bromide (1 mmol), morpholine (2 mmol) and 3-nitroben-
zene azide (1 mmol) in H2O (3 mL) as the solvent, in the presence of 2.5 mol% of
the catalyst and 5 mol% of sodium ascorbate, an 80% reaction yield was obtained
(Table 1, entry 11).
In this reaction, we used two equiv. of morpholine, one as reactant and the
other as base. The reaction was signifcantly infuenced by the nature of the base
employed. Among the bases tested, K2CO3 proved to be the most efcient one, giv-
ing a cleaner product and an excellent reaction yield (Table 1, entries 1–6). The
efects of the solvent and the amount of the catalyst used were also studied. We
screened EtOH, CH3CN, acetone, CH2Cl2, toluene, and water in the presence of an
organic or inorganic base. Among the solvents tested, water was found to be the most
suitable. Increasing or decreasing the amount of copper catalyst prolonged the reac-
tion time and decreased the reaction yield. The optimum reaction conditions for the
multi-component synthesis of 1,2,3-triazoles was 2.5 mol% of PVC–EDA–Cu(II)
and 5 mol% of sodium ascorbate in the presence of K2CO3 at room temperature in
Fig. 2 SEMs for PVC (a) and
PVC–EDA–Cu2+ (b)
1 3

PVC-supported ethylenediamine-copper(II) complex: a…
Table 1 Optimization reaction of propargyl bromide, 3-nitrobenzene azide, and morpholine using different bases and
solvents
Entry
Solvent
Base
Catalyst load- T (°C)
Time (min)
Yield (%)
ing (mol%)
1
2
3
4
5
6
7
8
H2O
H2O
EtOH
EtOH/H2O(1:1)
Acetone
CH3CN
CH2Cl2
Toluene
THF
H2O
H2O
EtOH
EtOH/H2O (1:1)
Acetone
CH3CN
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Et3N
K2CO3
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
2.5
1.5
3.0
RT
50
30
30
30
30
60
60
60
60
60
30
60
60
60
60
60
30
30
91
90
85
88
80
75
70
50
65
60
80
75
85
80
60
70
88
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
RT
9
K2CO3
Et3N
10
11
12
13
14
15
16
17
Morpholine
Morpholine
Morpholine
Morpholine
Morpholine
K2CO3
H2O
K2CO3
Reaction conditions: morpholine (1.0 mmol), propargyl bromide (1.0 mmol), 3-nitrobenzene azide
(1 mmol), and PVC–EDA–Cu+2 in solvent
water (Table 1, entry 1). To study the scope of this protocol, reactions of a variety
of aromatic azides and amines such as morpholine, piperidine, and aniline with pro-
pargyl bromide were run, and a library of substituted 1,2,3-triazoles was obtained
(Table 2). Both the electron-withdrawing and electron-donating substituents on the
aromatic azide were well tolerated. Methyl, nitro, and chloro produced the desired
products with high reaction yields. The position of the substituent had no signifcant
efect on the reaction yield.
The pure products were isolated by careful crystallization in EtOH/H2O, avoid-
ing tedious work-up and column chromatography for product purifcation. Structural
assignments of the new compounds were based on the NMR spectroscopic data and
mass analysis.
The reusability of the catalyst was also examined (Table 3, entries 1–4). After
each run, the resulting precipitate was washed with water and then dried. Hot
1 3

A. Keivanloo et al.
Table 2 Synthesis of 1,2,3-triazoles by reaction of propargyl bromide, aryl azides, and amines in water
Entry
1
Product
Time (min)
30
Yielda (%)
91 (32)b
4a
4b
4c
4d
4e
2
3
4
5
30
30
40
50
91
93
85 (32)
88 (32)
6
7
4f
50
40
94
86
4g
8
4h
4i
40
40
40
88
9
85 (32)
89
10
4j
Reaction conditions: amine (1.0 mmol), propargyl bromide (1.0 mmol), aromatic azide (1 mmol), and
PVC–EDA–Cu+2 (2.5 mol%) in H2O
aIsolated yield
bReference
1 3

PVC-supported ethylenediamine-copper(II) complex: a…
ethanol was added to the solid, and the product was extracted. The residue (catalyst)
was washed twice with hot EtOH and reused. This catalyst was reusable, although
gradual decline in its activity was observed.
The synthesized compounds 4a, 4d, 4e, 4f, 4h, and 4i were screened for their
in vitro antibacterial activity against Gram-positive and Gram-negative bacte-
rial strains including Micrococcus luteus (M. luteus), Pseudomonas aeruginosa
(P. aeruginosa), and Bacillus subtilis (B. subtilis) using the well-difusion method
(Table 4). Tetracycline and DMSO were used as positive and negative controls,
which showed no activity against these bacterial strains.
The antibacterial activity of the synthesized compounds was screened at a con-
centration of 1000 μg/mL in DMSO. The values were expressed in millimeters
(mm). According to the results tabulated in Table 4, compound 4f was inactive
against all three bacterial strains, compounds 4h and 4i possessed antibacterial
activities against P. Aeruginosa and M. luteus, and only compound 4i was active
against all three bacterial strains. Moreover, the antibacterial activity of compound
4d against P. aeruginosa was comparable to the standard drug, tetracycline.
Table 3 Condensation of
amines, propargyl bromide,
aromatic azides, and PVC–
EDA–Cu+2 using recycled
catalysts
Entry
Number of cycles
Yielda (%)
1
2
3
4
5
1
2
3
4
5
90
87
86
74
71
Reaction conditions: amine (1.0 mmol), propargyl bromide
(1.0 mmol), aromatic azide (1 mmol), recycled catalyst (2.5 mol%),
10 min
aIsolated yield
Table 4 Antibacterial activities
of selected compounds
(1000 μg mL−1) as inhibition
zone in mm
Entry
Compound
P. aeruginosa M. luteus
B. subtilis
1
2
3
4
5
6
7
8
4h
8
9
–
9
8
–
7
–
–
15
4i
9
8
4d
12
–
–
–
4f
4e
–
–
4a
–
–
10
–
DMSO
Tetracycline 13
41
1 3

A. Keivanloo et al.
Conclusion
We have developed an efcient, clean, and environmentally friendly procedure for
the synthesis of 1,2,3-triazoles via the multi-component reaction of propargyl bro-
mide, aromatic azides, and amines in water at room temperature in good-to-excellent
yields. This protocol utilizes the PVC-supported copper(II) complex as a heteroge-
neous catalyst, in mild reaction conditions, and does not require tedious work-up
and column chromatography for product purifcation. The other advantages of this
method are short reaction time, using water as a green solvent, and the capability of
recovery and reuse of the catalyst.
Acknowledgement The authors wish to express their thanks to the Research Council of Shahrood Uni-
versity of Technology for the fnancial support of this research work.
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