Malaysian Polymer Journal, Vol. 9 No. 2, p 70-77, 2014
Available online at www.cheme.utm.my/mpj
REMOVAL OF CU2+, Ni2+ AND Zn2+ METAL IONS FROM WATER BY
HYDROXYL TERMINATED S-TRIAZINE BASED DENDRIMER
Rinkesh Patel, Hema Patel, Dhaval Gajjar and Pravinkumar M. Patel *
Industrial Chemistry Department, V.P. & R. P. T. P. Science College affiliated to Sardar Patel University, Vallabh
Vidhyanagar, Gujarat, INDIA
Corresponding author’s email: [email protected]
ABSTRACT: Treatment of waste water containing heavy metal ions is one of the major global problems. In
overview in recent techniques, adsorption technique is one the low cost methods used to remove heavy metal ions
from relatively low concentrations from aqueous solutions. Dendrimer are fourth a new class of polymeric
architectures. We have applied dendrimers as low cost adsorbent for metal ions. In this paper, hydroxyl
terminated s-triazine based dendrimers G1, G2 and G3 terminated with 8, 32 and 128 hydroxyl groups were used
as adsorbents in a series of experiment to remove Cu2+, Ni2+ and Zn2+ from aqueous solution evaluated by EDTA
method. Effect of time, pH and generation on the metal ion uptake was studied. It was found that 12 h was
optimum time for metal ion uptake and metal ion uptake was increased with increase in pH and generation of
dendrimer. Adsorption for Cu2+ ions was maximum for all dendrimer generations whereas minimum for Zn 2+ ions.
Parent G3 dendrimer and G3 dendrimer metal-complexes were further characterized by FT-IR and Thermo
Gravimetric Analysis (TGA) to determine the active binding site for metal ion uptake and to confirm the presence
of metal in the final metal containing dendrimer respectively.
KEYWORDS: Dendrimer; Water remediation; Thermo gravimetric analysis; Divergent method; Triazine trichloride.
1.0 INTRODUCTION
Dendritic macromolecules or polymers are fourth new
architecturing class of polymer with structure resembles
to “tree” [1]. One of the members of the above class of
polymer is a dendrimer which have perfectly branched
structure and monodispersity compared to other
polymers in same class [2]. Since their invention in 1979
[3] dendrimer has exhibited their potential in various
fields of applications such as drug delivery [4, 5], drug
solubilisation [6, 7], water remediation [8], sensing
application [9] and cancer therapy [10].
Contamination of heavy metal ions such as Cu, Ni, Zn,
Cr, Cd, Hg, Pb in water resources has been increased due
to various industrial activities [11]. Most of these metal
ions are soluble in water and either toxic or carcinogenic
in nature. If the concentration of these metal ions
increases above specific limit, contamination of these
metal ions cause hazards to humans and aquatic life [1213]. Treatment of waste water containing heavy metal
ions is one of the most crucial problems [14]. Currently,
waste water containing heavy metal ions can be treated
by techniques such as chemical precipitation [15],
electro-dialysis [16], photo-dialysis [17], membrane
technique [18] and adsorption [19] etc. Amongst them,
adsorption is most commonly used technique because of
several limitations associated with other techniques such
as high cost, production of toxic sludge, the high energy
requirement can be avoided. Adsorption technique also
has an advantage that it removes metal ions from lower
concentrations from their aqueous solution [20].
Common adsorbents used for the said purpose are
activated carbon [21], minerals [22], polymer resins [23],
agricultural waste [24] etc.
In previous work, we have reported synthesis of hydroxyl
terminated s-triazine based dendrimer up to generation
three
using
N,N’-bis(4,6-dichloro-1,3,5-triazin-2yl)hexane-1,6-diamine [6] as core. Dendrimer was fully
characterized by spectral techniques and potential of
synthesized dendrimer as solubility enhancers of drug
was evaluated [6]. We have found that recent reports on
the removal of heavy metal ions from water by
dendrimer [25, 26] which encouraged us to evaluate
candidature of synthesized dendrimer for removal of
heavy metal ions from water.
In this paper, we have reported sorption behavior of
different generation of triazine based dendrimer (G1, G2
and G3) for removing heavy metal ions such as Cu2+, Ni2+
and Zn2+ from aqueous solutions by EDTA titration.
Study of parameters such as time, pH and generation on
the metal ion uptake was also reported. Pure generation
three dendrimer (G3) and metal ion containing
dendrimer (G3-Cu, G3-Ni and G3-Zn) were further
characterized by FT-IR to evaluate binding site in
dendrimer for metal ion adsorption and by Thermo
gravimetric analysis (TGA) to confirm the presence of
metals in final metal ion containing dendrimer.
2.0 EXPERIMENTAL
2.1. Materials
Cyanuric Chloride (Triazine trichloride), hexane1,6diamine, acetone, dichloromethane and methanol were
purchased from Sigma-Aldrich (India) Ltd. Nickel nitrate
Patel, R. et al. Malaysian Polymer Journal, Vol. 9, No. 2, p 70-77, 2014
(Ni(NO3)2.6H2O), copper nitrate (Cu(NO3)2.6H2O), zinc
nitrate
(Zn(NO3)2.6H2O),
sodium
hydroxide
and
hydrochloric acid were purchased from Merck (India) Ltd.
All the reagents and solvents for the synthesis and
analysis were used as received.
2.2. Analytical Methods
FTIR studies were carried out in the range of 250–4000
cm−1 using Perkin Elmer-Spectrum RX-FTIR spectrometer
instrument through KBr disc and pellet method or nujol
mull method. 1H-NMR and 13C-NMR spectra were recorded
at 400 MHz in Brucker Avance II 400 (Germany) using
TMS as internal standard. Thermo gravimetric analysis
was performed on Perkin Elmer Pyris-1 TGA instrument
with heating rate of 10˚C/min and in nitrogen
atmosphere. Mass spectra were recorded on Waters
Micromass Q-ToF Micro (USA) instrument equipped with
ESI.
2.3. Synthesis of Dendrimer [6]
2.3.1. Synthesis of N,N’-bis(4,6-dichloro-1,3,5-triazin-2yl)hexane-1,6-diamine (Core)
Cyanuric Chloride (0.02mmol) was dissolved in
dichloromethane and kept in an ice bath. A solution of
hexane 1,6-diamine (0.01mmol) containing sodium
hydroxide (0.02 mmol) in water was added drop wise in
the solution of cyanuric chloride at 0-5 °C with stirring.
The solution was stirred at 0-5 °C for 2 hrs. Then the
solution was filtered, washed with methanol and acetone
and dried under vacuum: A white colored solid was
formed.
Yield, 83%; FT-IR (KBr, cm-1) ν: 3281(N-H), 2884,
2779(aliphatic C-H), 1722, 1624(C=N of triazine), 844,
796(C-Cl); 1H-NMR (400MHz, DMSO-d6) δ ppm: 1.28981.3558 (m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N), 1.49411.5383
(m,4H,N-CH2-CH2-CH2-CH2-CH2-CH2-N)
3.24453.2881(m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N); 13C-NMR
(75MHz, DMSO-d6) δ ppm: 25.20 (N-CH2-CH2-CH2-CH2CH2-CH2-N),
30.52
(N-CH2-CH2-CH2-CH2-CH2-CH2-N),
40.52(N-CH2-CH2-CH2-CH2-CH2-CH2-N), 168.34 (Triazine CN), 169.40(Triazine C-Cl); Anal. Calcd. for C12H14Cl4N8: C,
34.97; H, 3.42; N, 27.19 found C, 35.02; H, 3.49; N, 27.26.
2.3.2. Synthesis of generation 1 dendrimer (G1)
N,N’-bis(4,6-dichloro-1,3,5-triazin-2-yl)hexane-1,6-diamine
(0.01mmol)
was
dissolved
in
an
excess
of
diethanolamine (0.04mmol) which was used as both
solvent and reactant. The resulting mixture was refluxed
for 2 hrs. After cooling, it was dispersed and washed by
acetone repeatedly to give generation 1 dendrimer which
was light brown colored.
Yield.75%; FTIR (KBr, cm-1) ν: 3364 (O-H), 2941 (aliphatic
C-H), 1668 (C=N of triazine), 1063 (C-O); 1H-NMR
(400MHz, D2O) δ ppm: 1.3138-1.3358 (m, 4H, N-CH2-CH2CH2-CH2-CH2-CH2-N), 1.4945- 1.5145 (m, 4H, N-CH2-CH2CH2-CH2-CH2-CH2-N), 3.4191- 3.4381 (m, 4H, N-CH2-CH2CH2-CH2-CH2-CH2-N) 3.5785-3.6151 (m, 16H, N-CH2-CH2OH), 3.7801-3.8145 (m, 16H, N-CH2-CH2-OH); 13C-NMR
(75MHz, D2O) δ ppm: 25.20 (N-CH2-CH2-CH2-CH2-CH2-CH2N), 30.52 (N-CH2-CH2-CH2-CH2-CH2-CH2-N), 40.52 (N-CH2CH2-CH2-CH2-CH2-CH2-N), 58.04 (N-CH2-CH2-OH), 61.04
(N-CH2-CH2-OH), 168.04(Triazine C-N), 169.90 (triazine C-
N-(CH2-CH2-OH)2); Anal. Calcd. for C28H54N12O8: C, 48.97; H,
7.92; N, 24.47; Found C, 49.02; H, 7.98; N, 24.50.
2.3.2. Synthesis of generation 1.5 dendrimer (G1.5)
Cyanuric Chloride (0.08mmol) was dissolved in
dichloromethane and kept in an ice bath. A solution of
G1 dendrimer (0.01mmol) containing sodium hydroxide
(0.08 mmol) in water was added drop wise in the solution
of cyanuric chloride at 0-5 °C with stirring. The solution
was stirred at 0-5 °C for 2 hrs and refluxed for 6 hrs.
Then the solution was filtered, washed with methanol
and acetone and dried under vacuum: A white colored
solid was formed.
Yield 84%; FT-IR (KBr, cm-1) ν: 3214 (N-H), 2834, 2832,
2780 (aliphatic C-H), 1779, 1753, 1717(C=N of triazine),
1061(C-O), 786 (C-Cl); 1H-NMR (400MHz, D2O) δ ppm:
1.3138-1.3358 (m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N),
1.4945- 1.5145 (m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N),
3.4191-3.4381 (m, 4H, CH2-NH); 3.8585-3.9350 (m, 16H,
N-CH2-CH2-O-Tri), 4.0301-4.0832 (m, 16H, N-CH2-CH2-OTri); 13C-NMR (75MHz, D2O) δ ppm: 25.20 (N-CH2-CH2-CH2CH2-CH2-CH2-N), 30.52 (N-CH2-CH2-CH2-CH2-CH2-CH2-N),
41.47
(N-CH2-CH2-O-tria),
61.04
(N-CH2-CH2-O-tria),
163.01 (Triazine C-N), 166.66 (Triazine C-N-(CH2-CH2-O)2), 170.18 (Triazine C-O), 172.28 (Triazine C-Cl); Anal.
Calcd. for C52H46Cl16N36O8: C, 33.39; H, 2.48; N, 26.96;
Found: C, 34.02; H, 2.50; N, 27.01.
2.3.4. Synthesis of generation 2 dendrimer (G2)
Generation 1.5 dendrimer (0.01mmol) was dissolved in
an excess of diethanolamine (0.16 mmol) which was used
as both solvent and reactant. The resulting mixture was
refluxed for 2 hrs. After cooling, it was dispersed and
washed by acetone repeatedly to give generation 2
dendrimer which was light brown colored.
Yield 75%; FTIR (KBr) ν: 3389(O-H), 2939, 2950(aliphatic
C-H), 1671, 1619(C=N of triazine), 1068 (C-O).; 1H-NMR
(400MHz, D2O) δ ppm: 1.3158-1.3355 (m, 4H, N-CH2-CH2CH2-CH2-CH2-CH2-N), 1.4984-1.5138 (m, 4H, N-CH2-CH2CH2-CH2-CH2-CH2-N), 3.4191-3.4381 (m, 4H, CH2-NH),
3.6743-3.7837 (m, 16H, N-CH2-CH2-OH), 3.8126-3.8970
(m, 16H, N-CH2-CH2-OH), 3.9803-4.0433 (m, 64H, N-CH2CH2-O-tri), 4.0917-4.1672 (m, 64H, N-CH2-CH2-O-tri); 13CNMR (75MHz, D2O) δ ppm: 25.70 (N-CH2-CH2-CH2-CH2-CH2CH2-N), 30.31 (N-CH2-CH2-CH2-CH2-CH2-CH2-N), 40.81 (NCH2-CH2-CH2-CH2-CH2-CH2-N), 60.81 (N-CH2-CH2-O-tria),
61.28 (N-CH2-CH2-OH), 63.78 (N-CH2-CH2-O-tria), 65.80 (NCH2-CH2-OH), 163.66(Triazine C-N), 168.66(Triazine C-N(CH2-CH2-O-)2), 170.18(Triazine C-O), 172.21(Triazine CN(CH2-CH2-OH)2); Anal. Calcd. for C116H206N52O40: C, 46.92;
H, 6.99; N, 24.53; Found C, 47.01; H, 7.02; N, 24.59.
2.3.5. Synthesis of generation 2.5 dendrimer (G2.5)
Cyanuric Chloride (0.32mmol) was dissolved in
dichloromethane and kept in an ice bath. A solution of
G2 dendrimer (0.01mmol) containing sodium hydroxide
(0.32 mmol) in water was added dropwise in the solution
of cyanuric chloride at 0-5 °C with stirring. The solution
was stirred at 0-5 °C for 2 hrs and refluxed for 6 hrs.
Then the solution was filtered, washed with methanol
and acetone and dried under vacuum: A white colored
solid was formed.
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Yield: 70%; FT-IR (KBr, cm-1) ν: 3280 (N-H), 2852, 2819
(aliphatic C-H), 1750, (C=N of triazine), 1045(C-O), 787
(C-Cl); 1H-NMR (400MHz, DMSO-d6) δ ppm: 1.3118-1.3351
(m, 4H, m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N), 1.49841.5150 (m, 4H, N-CH2-CH2-CH2-CH2-CH2-CH2-N), 3.41513.4389 (m, 4H, CH2-NH), 4.0153- 4.1380 (m, 16H, N-CH2CH2-O-tri), 4.2168-4.2929 (m, 16H, N-CH2-CH2-O-tri); 13CNMR (75MHz, DMSO-d6) δ ppm: 25.20 (N-CH2-CH2-CH2CH2-CH2-CH2-N), 30.05 (N-CH2-CH2-CH2-CH2-CH2-CH2-N),
40.45 (N-CH2-CH2-CH2-CH2-CH2-CH2-N), 60.06 (N-CH2-CH2O-tria), 61.23 (N-CH2-CH2-OH), 63.30 (N-CH2-CH2-O-tria) ,
65.53 (N-CH2-CH2-OH), 164.11 (Triazine C-N), 166.41
(inner C-N-(CH2-CH2-O-)2), 168.81 (outer Triazine C-O),
171.74 (outer C-N-(CH2-CH2-O-)2), 172.57(outer C-Cl),
174.94
(inner
triazine C-O); Anal
Calcd.
for
C212H174Cl64N148O40 : C, 33.05; H, 2.28; N, 26.91; Found C,
33.12; H, 2.30; N, 26.99.
2.3.6. Synthesis of generation 3 dendrimer (G3)
Generation 2.5 dendrimer (0.01mmol) was dissolved in
an excess of diethanolamine (0.64 mmol) which was used
as both solvent and reactant. The resulting mixture was
refluxed for 2 hrs. After cooling, it was dispersed and
washed by acetone repeatedly to give generation 1
dendrimer which was light brown colored.
Yield: 71 %; FT-IR (KBr, cm-1) ν: 3368 (O-H), 2947, 2872
(aliphatic C-H), 1639 (C=N of triazine), 1033 (C-O); 1HNMR (400MHz, D2O) δ ppm: 1.3138-1.3353 (m, 4H, m, 4H,
N-CH2-CH2-CH2-CH2-CH2-CH2-N), 1.4954-1.5181 (m, 4H, NCH2-CH2-CH2-CH2-CH2-CH2-N), 3.4144-3.4333 (m, 4H, CH2NH), 3.6833-3.7574 (m, 264H, N-CH2-CH2-OH), 3.88293.9243 (m, 264H, N-CH2-CH2-OH) 4.0953- 4.1880 (m, 80H,
N-CH2-CH2-O-tri), 4.2432-4.3168 (m, 80H, N-CH2-CH2-Otri); 13C-NMR (75MHz, D2O): 25.50 (N-CH2-CH2-CH2-CH2CH2-CH2-N), 30.14 (N-CH2-CH2-CH2-CH2-CH2-CH2-N), 40.44
(N-CH2-CH2-CH2-CH2-CH2-CH2-N), 59.92 (N-CH2-CH2-O-tria),
60.60 (N-CH2-CH2-OH), 63.39 (N-CH2-CH2-O-tria) , 66.69 (NCH2-CH2-OH), 168.11(Triazine C-N), 169.99(inner C-N(CH2-CH2-O-)2), 171.55(outer Triazine C-O), 175.81(outer
C-N-(CH2-CH2-O-)2), 177.28 (outer C-N-(CH2-CH2-O-)2,
179.11(Triazine C-O); Anal Calcd. for C468H814N212O168: C,
46.46; H, 6.78; N, 24.54; Found C, 46.51; H, 6.80; N,
24.59; ESI-Mass: Molecular Wt. 12086 found (M+1):
12087.
2.4. Metal ion uptake
Aqueous solution of 3 mmol metal salt [Ni(NO3)2.6H2O,
Cu(NO3)2.6H2O, Zn(NO3)2.6H2O] in 20 mL water was added
to 200 mg of dendrimer(G1, G2 and G3) separately. The
solution pH was set at 4, 7 and 9 by using buffers. The
mixture was shaken in a thermostatic water-bath shaker
which operated at 25 ˚C. To study effect of time, 200 mg
of dendrimer was allowed to react with 20 ml metal salt
solution for fixed time intervals. The metal-dendrimer
complexes were collected by filtration, washed with
aqueous solution of the same pH to remove noncomplexed metal ions and dried in vacuum oven. The
filtrate and washings were collected to 50 ml volumetric
flask and titrated against ethylene diamine tetracetic acid
disodium (EDTA-2Na) salt using Murexide indicator to
determine amount of metal adsorbed by dendrimer [8].
3.
Result and Discussion
3.1 Dendrimer synthesis and Characterization
Dendrimer was synthesized from N,N’-bis(4,6-dichloro1,3,5-triazin-2-yl)hexane-1,6-diamine as core [6, 27] using
temperature controlled nulcleophillic substitution of
triazine trichloride. N,N’-bis(4,6-dichloro-1,3,5-triazin-2yl)hexane-1,6-diamine was synthesized in first step using
triazine trichloride and hexane1,6-diamine as starting
materials at low temperature to ensure that only one
chlorine atom of triazine trichloride was substituted by a
diamine. A core was then reacted with diethanolamine
which was used as both solvent and reactant to give
generation 1 (G1) dendrimer. The above two steps were
iterated until generation 3 dendrimer was obtained.
Dendritic generations were fully characterized by
spectral techniques such as FTIR, 1H-NMR, 13C-NMR,
Electrospray ionization mass spectrometry and elemental
analysis reported elsewhere [6, 27].
3.2 Metal ion uptake
Sorption capacities full generation dendrimers G1, G2
and G3 terminated with 8, 32,128 hydroxyl groups res
for heavy metal ions such as Cu2+, Ni 2+ and Zn 2+ was
studied in relation to time, pH and generation number.
3.2.1 Effect of time
To investigate effect of time factor [Figure 1.], a known
amount of dendrimer was added to metal ion solutions
and solutions were stirred at different time periods of
6h, 12h, 18h and 24h at pH 7, then resulting solutions
were filtered and amount of metal ion uptake was
determined by EDTA method. It was observed that 12 h
was the optimum time for equilibrium [26]. Metal ion
uptake was increased with increase in time after 12 h,
uptake was nearly constant. Therefore, further studies
were carried out at 12 h time.
3.2.2. Effect of pH
Effect of pH factor metal ion uptake by dendrimer
generations were studied by executing metal ion uptake
experiments as pH 4, 7 and 9. The results are furnished
in Fig 2. It was observed that for all the generations
metal ion uptake increased with increase in pH. As pH,
increased, protonation of ligands decreased which led to
higher metal uptake [26].
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Scheme 1: Synthetic route to s-triazine based dendrimer
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Figure 2: Effect of pH and generation on metal ion
uptake by A) G1 dendrimer B) G2 Dendrimer and C) G3
dendrimer
3.3.1. Infrared Spectroscopy
IR spectrum of pure G3 dendrimer showed (Table 1)
absorption band at 3368 cm-1 for O-H stretching of
hydroxyl groups. After complexion with Cu ions, Ni ions
and Zn ions the said absorption band shifted to 3438,
3423 and 3405 cm-1 respectively for G3-Cu, G3-Ni and
G3-Zn. While other prominent bands for C-H stretching,
C-O stretching and C-N stretching remained at same
value [Figure 3.]. This denotes that hydroxyl group must
be the active binding site for metal ion uptake [26, 8].
Figure 1: Showed plot of metal ion uptake by A) G1
dendrimer, B) G2 dendrimer & C) G3dendrimer v/s time
at pH 7.
3.2.3. Effect of generation number
It was also evident from Fig 2 that with increase in
generation number, metal ion uptake was increased. As
generation number of dendrimer increased, number of
terminal hydroxyl groups responsible for metal ion
uptake was increased. Also with increase in generation of
dendrimer, size of the dendrimer also increased. Hence,
due to increase in surface group and size of dendrimer,
metal ion uptake increased.
The result was in
accordance to previous results [8]. So, overall metal ion
uptake was increased with increase in pH, generation
number. It was also observed that uptake of Cu ions was
maximum where as it was minimum for Zn ions.
3.3. Characterization of metal-dendrimer complexes
Generation 3 dendrimer and G3 dendrimer-metal
complexes were further characterized by IR and TGA to
confirm presence of metal in final metal containing
dendrimer.
Table 1: Prominent peaks in infrared spectroscopy for
pure G3 dendrimer and dendrimer metal complexes
G3 dendrimer
and dendrimer-metal
complex
G3
G3-Cu
G3-Ni
G3-Zn
FT-IR absorption bands(cm-1)
O-H
C-H
C-O
C-N
3368
3438
3423
3405
2847
2847
2847
2847
1033
1033
1033
1033
1639
1639
1639
1639
3.3.2 Thermo gravimetric Analysis
Pure generation 3 dendrimers and dendrimer containing
Cu, Ni and Zn were characterized by thermo gravimetric
analysis. TGA graph of G3 dendrimer (Fig. 4 A) showed
two stage thermal decomposition, in first stage G3 lost
18% wt. up to 150 °C due to bound moisture. In second
stage G3 dendrimer lost its remaining wt. ended up with
residual wt. of 4.034 % at 600°C. Dendrimer containing
metals such as G3-Cu, G3-Ni and G3-Zn showed similar
thermal behavior (Fig 4. B-D) but their final residual
weights were 14%, 13% and 12% respectively due to
formation of metal oxides. These confirmed presence of
metal in final metal containing dendrimer [26, 8] was
highest, Zn ions was least. Generation 3 dendrimer had
highest sorption capacity.
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Figure 3. FT-IR Spectrum of A) pure G3 dendrimer, B) G3 dendrimer containing Cu metal, C) G3 dendrimer containing Ni
metal and D) G3 dendrimer containing Zn metal
Figure 4: Thermo gravimetric Analysis Graphs of A) pure G3 Dendrimer, B) G3-Cu dendrimer, C) G3-Ni dendrimer and D)
G3-Zn dendrimer
4.
CONCLUSION
Synthesized hydroxyl terminated triazine based dendritic
architectures (G1-G3) were evaluated for removal of
heavy metal ions such as Cu, Ni and Zn from water. It
was found that the optimum time for metal ion uptake
for all dendrimer generations was found to be 12 h. With
increase in pH and generation number, metal ion uptake
was increased. Adsorption for Cu2+ ions was maximum
for all dendrimer generations whereas minimum for Zn 2+
ions. Infrared spectroscopy of G3 dendrimer and metal
containing dendrimer revealed that hydroxyl group was
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the active binding site for metal up take. TGA study of
dendrimer and metal containing dendrimer confirmed
presence of metal in final metal containing dendrimer.
5.
ACKNOWLEDGEMENT
The authors are grateful to The Principal, V. P. & R.P.T. P.
Science College for providing laboratory facility. Authors
are also grateful to U.G.C., New Delhi for funding this
research work. The authors acknowledge Sophisticated
Analytical Instrumentation Facility (SAIF), Punjab
University, Chandigarh, Sophisticated Instrumentation
Centre for Advanced Research and Testing (SICART),
Sardar Patel University, Vallabh Vidhyanagar and Central
Salt and Marine Chemicals Research Institute (CSMCRI),
Bhavnagar providing instrumentation facilities.
6.
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