Metal complexes of the nanosized ligand N-benzoyl-N′-(p-amino phenyl) thiourea: Synthesis, characterization, antimicrobial activity and the metal uptake capacity of its ligating resin

Article abstract of DOI:10.1016/j.molstruc.2015.07.049

The new nanosized N-benzoyl-N′-(p-amino phenyl) thiourea ligand H₂L was synthesized by nanoprecipitation method. The [Cu (H₂L)₂ Cl]·2H₂O, [Zn (H₂L)₂(OAc)₂], [Cd (H₂L)<

Full text of DOI:10.1016/j.molstruc.2015.07.049

Accepted Manuscript
Metal complexes of the nanosized ligand N-Benzoyl-N'-(p-amino phenyl) thiourea:
Synthesis, characterization, antimicrobial activity and the metal uptake capacity of its
ligating resin
Amel F. Elhusseiny, Ali Eldissouky, Ahmed M. Al-Hamza, Hammed H.A.M. Hassan
PII:
S0022-2860(15)30160-5
10.1016/j.molstruc.2015.07.049
MOLSTR 21704
DOI:
Reference:
To appear in: Journal of Molecular Structure
Received Date: 13 April 2015
Revised Date: 7 July 2015
Accepted Date: 24 July 2015
Please cite this article as: A.F. Elhusseiny A. Eldissouky, A.M. Al-Hamza, H.H.A.M. Hassan, Metal
complexes of the nanosized ligand N-Benzoyl-N'-(p-amino phenyl) thiourea: Synthesis, characterization,
antimicrobial activity and the metal uptake capacity of its ligating resin, Journal of Molecular Structure
(2015), doi: 10.1016/j.molstruc.2015.07.049.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Metal complexes of the nanosized ligand N-Benzoyl-N'-(p-amino
phenyl) thiourea: Synthesis, characterization, antimicrobial activity
and the metal uptake capacity of its ligating resin
AMEL F. ELHUSSEINY*, ALI ELDISSOUKY, AHMED M. AL-HAMZA,
HAMMED H.A.M. HASSAN
Faculty of Science, Chemistry Department, Alexandria University, P.O. Box 426-
Ibrahimia, 21321-Alexandria, Egypt, Alexandria, Egypt
*Corresponding author. .Tel:+201277766645, Fax: +2033911794
Email: amel_elhusseiny@sci.alexu.edu.eg
1

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Abstract
The new nanosized N-benzoyl-N'-(p-amino phenyl) thiourea ligand H L was
2
synthesized by nanoprecipitation method. The [Cu (H L) Cl].2H O, [Zn
2
2
2
(
H L) (OAc) ], [Cd (H L) Cl ] and [Hg (H L) Cl ] complexes were synthesized and
2 2 2 2 2 2 2 2 2
characterized by various physicochemical methods. Results revealed that the ligand
act as hypodentate and bonded to the metal ion via the sulphur atom forming
mononuclear non-electrolyte diamagnetic complex. Magnetic moment results
indicated a reduction of Cu (II) to Cu (I) during the coordination process. Thermal
studies demonstrated variable stabilities of the complexes and [Zn (H L) (OAc) ]
2
2
2
exhibited the highest thermal stability while [Hg (H L) Cl ] was volatile. The
2
2
2
prepared compounds were screened against different pathogenic microorganisms.
The ligand performed high antibacterial activity against certain bacterial strain
compared to its complexes, and the standard bacteriocide in use. The ligand was
successfully immobilized on modified Amberlite XAD-16 forming the hypodentate
ligating resin PS-SO -H L. The new resin was characterized and the extent of metal
2
2
adsorption reached maximum at pH 6.0 for Cu (II), Cd (II) and Ag (I), with an
-1
adsorption amount of 4.3, 4.0 and 3.7 mmolg respectively. The nanosized H L
2
represents a new category of promising adsorbent that would have a practical impact
on biological and water treatment applications.
Keywords: Hypodentate; Antimicrobial; Thermal; Ligating Resin; Metal sorption.
2

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1. Introduction
Metal pollutants in aquatic environments pose a severe threat to public health
and ecological systems [1, 2]. Considerable efforts have been made to develop
effective treatment techniques for removing heavy metal ions from water. Adsorption
is probably the most common method in practical use. Solid phase extraction (SPE)
is one of the most important preconcentration methodologies because of its
simplicity, flexibility to choose the solid phase, high preconcentration factor, low
consumption of the organic solvents, low cost and extraction time for sample
preparation [3-5]. SPE using coordinating resins is preferable over all other
separation techniques due to the selectivity, eco-friendliness, reusability and high
preconcentration factors [6,7 ]. The selectivity of coordinating resins for metal ions
mainly refers to the nature of the immobilized structure of the polymer matrix [8, 9].
Amberlite series [10, 11] have been found very promising applications as
coordinating resins due to their variable physical properties including porosity, high
surface area, chemical homogeneous nonionic structure and good adsorbent
properties for great amounts of uncharged compounds.
Thioureas are potentially very versatile ligands and able to coordinate to a
range of metal ions as neutral, monobasic or dibasic ligands [12]. Their derivatives
have found extensive applications in medicine, agriculture, analytical chemistry,
pharmaceutical [13], inhibitors in the corrosion field [14] and catalysts in chemical
reactions [15]. In addition, these compounds are known to exhibit a wide variety of
biological activities including antiviral, antibacterial, antifungal [16] and
antitubercular, herbicidal, insecticidal effect [17]. Aroyl thioureas are well-known
class of excellent ligands that have at least three potential donor atoms (N, O, S) in
complexation reactions [18]. For instance, 3-monosubstituted aroylthioureas [19-21],
the carbonyl group and the proton on the N3 engage in a strong hydrogen bond
interaction and united into a planar six-membered ring structure forming an “S”
shaped conformation of the C=O and C=S groups [22]. Reactions of aroylthiourea
10
with d metal (II) ions such as Zn (II), Cd (II), and Hg (II) have received renewed
attention due to their non-linear optical properties [23, 24].
3

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Herein we aim to synthesize a new type of nanosized hypodentate ligand and
examine its coordination toward Cu (II), Zn (II), and Cd (II) and Hg (II) ions. The
bacteriocidal and
fungicidal activities of the prepared compounds are tested.
Reaction of the ligand with modified Amberlite XAD-16 to produce the hypodentate
ligating resin [PS-SO -H L] and investigate its metal uptake capacity for ions of Cu
2
2
(
II), Cd (II) and Ag (I) is also described.
2
. Experimental
.1. Materials
2
Amberlite XAD-16 was obtained from Aldrich. The reagents ammonium
thiocyanat, benzoyl chloride, p-phenylenediamine, chlorosulphonic acid, copper (II)
chloride dihydrate, copper (II) nitrate trihydrate, cadmium (II) chloride dihydrate,
cadmium (II) sulfate tetrahydrate, mercury (II) chloride, silver (I) nitrate, zinc (II)
acetate dehydrate, ammonium chloride, nitric acid, sodium hydroxide and
monochloroacetic acid were purchased from Aldrich were of analytical grade and
used as received. The solvent acetonitrile (BDH-PROLABO), ethanol, acetone, 1,4-
dioxane (Aldrich), dimethylsulfoxide (DMSO, Aldrich) and diethyl ether were of
analytical grade quality and were used without further purification.
2.2. Physical measurements
Melting points were measured on Stuart SMP10 digital melting point
apparatus and are uncorrected. The molar conductivity measurements were carried
-3
out using HI 8033 HANNA conductometer at 25
for 1.00 x10 M solution in
DMSO. Digital Orion pH/ISE meter, was used for the pH measurements. The pH
values of the solutions were adjusted with monochloroacetic acid / acetate buffer in
the pH range of 2.5 to 4, acetate buffer in the pH range of 4 to 7, and ammonia–
ammonium chloride in the pH range of 7 to 10. Hydrochloric acid and sodium
hydroxide solutions were used to adjust the pH below 1.5 and above 7. Elemental
analyses were performed at the Micro Analytical Unit, Cairo University. Metal
analysis was determined by atomic absorption technique at the Institute of Graduate
Studies and Research, Alexandria University. Chemical compositions of metal
4

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complexes were determined by energy-dispersive X-ray spectroscopy (EDX) (JEOL-
JSM5300) at the E-Microscope Unit-Faculty of Science-Alexandria University.
Infrared spectra (IR, KBr pellets, 3 mm thickness) were recorded on a Perkin-Elmer
Infrared Spectrophotometer (FT-IR 1650). All spectra were recorded within the wave
-1
1
number range of 600-4000 cm at 25 C. HNMR spectra were recorded using JEOL
6
at 500 MH in DMSO-d and using TMS as an internal standard and the chemical
Z
shift in each case is given ppm. Absorption spectra were recorded with a UV 500
UV-vis spectrophotometer at room temperature as DMSO solutions with a sample
concentration of (2 mg, 10 mL). Magnetic susceptibility measurements were carried
out at room temperature in powder form on a Magway Sherwood products Model
MK1 magnetic susceptibility balance using a sealed off sample of MnCl solution as
2
a calibrant. Mass spectroscopy was performed at Faculty of Science, Kuwait
University. Differential thermo gravimetric (DTG) analyses were carried out in the
temperature range from (25-700 °C) in a steam of nitrogen atmosphere by a
Shimadzu DTG 60H thermal analyzer. The experimental conditions were: platinum
crucible, nitrogen atmosphere with a 30 ml/min flow rate and a heating rate 20
C/min. The (TG, DTG) analyses were carried out using SDTQ600-V20.5-Build-15
at the Institute of Graduate Studies and Research, Alexandria University. The
morphologies of nanosized ligand were observed by Scanning Electron Microscope
(SEM) (JEOL-JSM5300) at the E-Microscope Unit; Faculty of Science, Alexandria
University. The samples were sonicated in de-ionized water for 5 min and deposited
onto carbon coated copper mesh and allowed to air-dry before the examination.
Antimicrobial Screening tests were conducted at Faculty of Science, and Alexandria
University.
2
.3 Synthesis of N-Benzoyl-N'-(p-amino phenyle) thiourea (H L)
2
A solution of benzoyl chloride (4.6 g; 32.6 mmol) in acetonitrile (30 mL) was
added drop wise to a suspension of ammonium thiocyanate (2.5 g; 32.7 mmol) in
acetonitrile (30 mL) kept in ice bath with stirring for 1 h. The formed white
precipitate of aminoum chloride was filtered off. A solution of p-phenylenediamine
(
4 g; 32 mmol) in acetonitrile (30 mL) was added to the benzoyl isothiocyanate
filtrate) and stirred for 4 h, (Scheme 1). The resulting yellow precipitate was
(
5

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filtered off washed with 10 mL acetonitrile four times, followed by diethyl ether and
dried in a vacuum desiccator. The crude product was crystallized from 15-20 mL
ethanol to afford the product.
2
.4 Synthesis of nanosized H L
2
Benzoyl chloride dissolved (1 g; 7.1 mmol) in acetonitrile (50 ml) was added
to ammonium thiocyanate (0.53 g; 7.0 mmol) dissolved in the same solvent (50 ml).
The solution was kept in an ice bath for 1h. It was filtered and the precipitate was
further washed with acetonitrile (10 ml). To p-phenylenediamine (7.0 mmol)
dissolved in 110 ml acetonitrile/water (100 ml acetonitrile and 10 ml distilled water)
the filtrate was added in one portion and the resulting mixture was ultrasonicated for
4
h at 42 KHz. Centrifugation of the mixture for 15 min. at 4800g produced the
nanosized ligand as solid product. The product was washed successively using
ethanol followed by diethyl ether and dried in a vacuum oven at 60 °C.
2.5 Synthesis of metal Complexes (General Method)
A warm ethanol solution (15 ml) of the metal salt: CuCl2 2H O (0.62 g; 3.69
•
2
mmol), Zn (CH COO) 2
•
2H O (0.81g; 3.69 mmol), CdCl H O (0.67 g; 3.66 mmol)
•
3
2
2 2
and HgCl (1.00 g; 3.66 mmol) was added to H L (2.00 g; 7.38 mmol) in dioxan (20
2
2
ml). The mixture was refluxed for 2 h and the precipitate was collected by filtration,
subsequently washed with ethanol, diethyl ether and dried in a vacuum oven at 60
°
C.
2
.6 Synthesis of chlorosulfonated polystyrene resin PS-SO Cl
2
Chlorosulfonated polystyrene resin was synthesized according to the reported
method [25]. Amberlite XAD-16 (5 g) in CHCl (50 mL) was allowed to swell for 2
3
h then stirred with a mixture of chlorosulfonic acid (50 mL) and chloroform (50 mL)
for 24 h at room temperature. The mixture is then filtered off, washed thoroughly
°
with dry dichloromethane and dried in a vacuum at 60 C for 72 h. The obtained
polymer beads were refluxed in 50 mL CHCl solution containing 25 mL thionyl
3
chloride (SOCl ) for 12 h, filtered, washed and dried.
2
6

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2
.7 Synthesis of hypodentate ligating resin PS-SO -H L
2
2
The dried above mentioned chlorosulfonated polystyrene resin (1.5 g)
suspended in acetone (10 ml) was treated with H L (1.75 g) in acetone (20 ml). The
2
reaction mixture was refluxed for 48h. The product was filtered off, washed with
acetone (3x 15 ml) and diethyl ether (3x 15 ml) then dried under vacuum at 60 C for
24 h.
2.8 Synthesis of metal complexes of hypodentate ligating resin
The resin PS-SO -H L (4g) was added to a solution of metal salt Cu
2
2
(
NO ) •3H O, AgNO or CdSO 4H O (2g) in methanol (20 mL) after adjusting the
3 2 2 3 4 2
pH range to 5.0-6.0 using acetate buffer. The reaction mixture was refluxed for 24 h.
The obtained complex was filtered and washed by methanol (5 x 10 mL) followed
diethyl ether (10 x 10 mL), and then dried under vacuum at 60 °C for 24 h.
2.9 Metal ion uptake experiment using column method
The resin PS-SO -H L (500 mg) was immersed in double distilled water and
2
2
allowed to swell for 24 h then loaded between frets on a glass column (C10/10
Pharmacia, 10 cm x 10 mm). The glass column was treated with 30 ml of HNO (2.0
3
-1
mol L ) and then rinsed with water until acid free. A suitable aliquot of the sample
-1
solution containing 10 to 50 mg L of Cu (II), Ag (I) or Cd (II) was passed through
-1
the column after adjusting its pH between 1.5 to 8 at a flow rate 1.0 to 6.0 mL min
using a peristaltic pump. The column was washed with water to remove the free
metal ion and the adsorbed metal ions were stripped from the column with HNO3
-1
(
2.0 moll ) at the above mentioned flow rate. The metal uptake was calculated from
eq. (1), [25]:
-1
q1 = (C0 C ) V/m
mmol.g --------------- (1)
1
-1
Where V (l) is the volume of the solution in the flask; C and C (mmoll ) are
0
1
the concentration of the metal ion in the aqueous phase at start and equilibrium,
respectively, m is the mass of the ligating resin (g).
7

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2.10 Antimicrobial activity
The antimicrobial activity of the H L and its metal complexes was determined
2
using a modified Kirby-Bauer disc diffusion method [26]. All the synthesized
compounds were dissolved in DMSO to prepare a stock solution of 1 mg / ml. Stock
solution was aseptically transferred and twofold diluted to have solutions of different
concentrations. The antibacterial and antifungal activities of the test compounds were
done by a filter paper disc method [27] and the activities were determined by
measuring the diameters of the inhibition zone (mm). Media with DMSO was set up
as a control. All cultures were routinely maintained on NA (nutrient agar) and
incubated at 37 °C. The inoculums of bacteria were performed by growing the
culture in NA broth at 37°C for overnight. Approximately, 0.1 ml of diluted bacterial
or fungal culture suspension was spread with the help of spreader on NA plates
uniformly. Solutions of the tested compounds and reference drugs were prepared by
dissolving 10 mg of the compound in 10 ml DMSO. A 100 µL volume of each
sample was pipetted into a hole made in the center of the agar. Sterile 8 mm discs
(Himedia Pvt. Ltd.) were impregnated with test compounds. The disc was placed
onto the plate. Each plate had one control disc impregnated with solvent. The plates
were incubated at 37 °C for 18-48 h. Standard discs of Tetracycline and
Streptomycin (Antibacterial agents; 10 µg / disc) and Amphotericin B (Antifungal
agent; 10 µg / disc) served as positive controls for antimicrobial activity while filter
discs impregnated with 10 µL of solvent DMSO were used as a negative control.
3. Results and discussion
3.1. Synthesis and characterization
The basic principle of nanoprecipitation [28] as a nanosized preparation
method is based on the interfacial deposition of a product after displacement of a
semi-polar solvent, miscible with water, from a lipophilic solution. The nanosized
particle characteristics are influenced by the nature and concentration of their
components [29]. The process of particle formation in the nanoprecipitation method
comprises three stages: nucleation, growth, and aggregation. The separation between
8

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the nucleation and the growth stages is the key factor for uniform particle formation
[
30].
The nanosized N-benzoyl-N'-(p-amino phenyle) thiourea H L was prepared,
2
by reaction of benzoyl chloride with ammonium thiocyanate in acetonitrile. The
filtrate was added in one portion to p-phenylenediamine dissolved in a mixture of
acetonitrile / water (10:1). Ultrasonication followed by centrifugation furnished the
targeted adduct. The structure of the ligand was fully characterized by different
analytical methods and data are collected in tables 1and 2. The nanosized ligand was
obtained as a well-separated spherical particles and the average diameter was 181 nm
(standard deviation = 26). The average diameter of the particles was estimated from
SEM image (Fig. 1) and selected at random. The addition of a particular amount of
water to the reaction system was essential for formation of spherical particles [31-
35]. The tendency of spherical particle formation may be correlated to the dispersion
stability of particles in the reaction solution or the precipitation mechanism of the
particles [36].
<
Scheme 1: Synthesis of N-Benzoyl-N'-(p-amino phenyle) thiourea (H L)>
2
<
Table 1: Elemental analysis and physical data of H L and its metal
2
complexes>
<
Fig. 1: SEM image of the free nanosized ligand H L >
2
The reaction of H L with CuCl2.2H O, Zn (CH COO)2. 2H O CdCl2.H O and
2
2
3
2
,
2
HgCl furnished the corresponding complexes with the general formula
[M
H L) Xn]. mH O, where X = Cl or CH COO, n = 1 or 2 and m = 0 or 2. For
2 2
2
(
2
3
structural elucidations and comparison purposes, bulk production of free H L [36]
2
was considered. Analytical, molar conductance, and spectral studies reveal that the
obtained complexes are non-electrolyte and contain two ligand molecules. The
complexes are air-stable, non-hygroscopic and soluble in both DMSO and DMF.
9

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3.1.1. FTIR Spectroscopy
The FTIR bands of the ligand H L and its metal complexes are given in table
2
2
. The spectrum of H L displays bands at ν 3465-3365, ν 3292-3231, ν 3185-3125, ν
2
-1
3
168-2999, ν 1673-1669, ν 1568-1521 and ν 1272-1254 cm assigned to ν (NH ), ν
2
'
(
N-H), ν (N'-H), ν (CH), ν (C=O), δ (N-H, thioamide band I) and ν (C=S),
-1
−1
respectively. Bands of ν (N-H) above 3200 cm while ν (N′-H) above ν 3000 cm
could be referred to the intramolecular hydrogen bonding N′–H…O=C and / or
trans–cis inter-conversion of benzoyl thiourea. The intramolecular hydrogen bond of
C=O and thiourea forms stable six-membered ring conformation [37]. The lack of ν
-1
SH around 2500-2600 cm confirmed the absence of the thiol (N=C-SH) tautomeric
form and pointed out to the fact that the ligand exists in the thioketo-amine [38]. The
-1
-1
-1
bands at 1165-1147cm , 1381-1327 cm and 943-883 cm are assigned to ν
asym
(NCN') thioamide band II, νsym (NCN') thioamide band III, and thioamide band IV,
respectively, [39-41]. The ν (C=O) band appeared at relatively lower wavenumber
-1
than the ordinary carbonyl absorption (1700 cm ) which may be attributed to the
either the intramolecular hydrogen bond and/or the conjugated resonance interactions
between the carbonyl and the phenyl ring [40, 41].
The absorption pattern for all complexes exhibited a shift to a high
−
1
wavenumber for those bands above 3200 cm suggesting the weakening of the
hydrogen bond interaction [36]. The positive shift of ν(N-H) and ν (N'-H) signifies
that the studied ligand is not an N-bonded. The ν C=O remains either unchanged or
upward shifted indicating non-bonding nature [36]. The coordination of S atom
causes ligand-metal charge transfer, which reduces the double bond character of the
C=S bond and allows a lower frequency shift of the thioimide band (IV). In addition,
the N C bond gains electron density, which raises its bond order and change the
frequency of fundamentals thioamide bands I–III (Table 2). The chelating bidentate
acetate ion in zinc complex [Zn (H L) (OAc) ], was supported by the separation
2
2
2
-
-
values
(
=
-
) where the magnitude of ( ) was comparable to
s(COO )
as(COO )
the values cited for the bidentate character of acetate group [42].
<
Table 2: FT-IR and UV-vis spectra of H L and its metal complexes>
2
1
0

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3.1.2. Magnetic moment and Electronic absorption spectra
The electronic spectra of the ligand H L and its metal complexes were recorded
2
-3
at 1.00 x 10 M DMSO solution in the range 250–900 nm and data are recorded in
table 2. The spectrum of the ligand exhibited one absorption band at 280 nm
attributed to the π-π* transition of aromatic rings, whereas the metal complexes
exhibited maximum intense bands in the range 280–290 nm ascribed to charge
transfer from the filled d-orbital metals to the π* system of the ligand [36].
Magnetic susceptibility measurements of metal complexes were carried out in
the solid state at room temperature. The effective magnetic moment value of zero for
Cu (H L) Cl].2H O, [Zn (H L) (OAc) ], [Cd (H L) Cl ] and [Hg (H L) Cl ]
2
2
2
2
2
2
2
2
2
2
2
2
1
0
complexes indicated their diamagnetic property in accordance with the d
configuration.
Furthermore, the absence of unpaired electrons for copper complex suggested
Cu (II)→Cu(I) reduction upon complexation with the oxidation of the ligand and or
strong magnetic exchange interaction [36]. Keeping in view, the absence of
electronic transition band at 370 nm ruled out direct Cu-Cu bonding which leads to
the quenching of the magnetic moment of the copper (II) complexes. The higher
affinity of sulfur to Cu (I) seems to play a role in the reduction of Cu (II) to Cu(I). A
plausible explanation is that the synthesized benzoyl thiourea derivative may be
oxidized to disulfide and Cu (II) is reduced to Cu (I) which remains in solution as a
complex with acetonitrile. At the same time, intramolecular hydrogen bonds of the
type NH•••Cl may be assumed to contribute to the stabilization of the Cu (I)
complexes [36]
3.1.3. NMR Spectra
1
H-NMR spectrum of the ligand unambiguously confirmed the presence of
three tautomers in 3:1:0.5 ratios, (Fig.2). The thioamide proton of the tautomers
resonated at 12.61, 12.56, 12.34 ppm, while that of the amide proton appeared at
11.59, 11.55, 11.37 ppm, respectively. Aromatic protons resonated at 7.98 (2d, 2H, J
=
7.65, arom), 7.80 (d, 2H, J = 8.1 Hz, arom), 7.78-7.68 (m, 1H, arom), 7.64 (2d, 1H,
1
1

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J = 7.60, 8.1 Hz, arom), 7.56 (d, J = 7.15 Hz, arom, minor isomer), 7.51 (2d, 2H, J =
7.65 Hz, arom), 7.25 (2d, 1H, J = 8.1, 7.6 Hz, arom), respectively.
The conformation around the amidic group has been studied [43]. Several
conformations are feasible for this kind of compound, depending on the dihedral
values around the aroyl-N bond and the adjacent C−N−C bond [44]. In general, the
local opposite orientation between the C=O and C=S bonds preferred the S-shape
[
45] in 1-aroyl-3-substituted thiourea derivatives, (Fig.3) where the C=O and H-N
groups form a pseudo-six-membered ring via an intramolecular hydrogen bond.
Thus, it is likely that the disfavored anticlinal geometries U- or M-forms changed
their conformations to the highly stable S-shape by simple rotations around C(O)-N
or C(S)-N bonds, respectively, similar to that related thiocarbamate species [ 45-48].
1
<
Fig. 2: H-NMR spectra of: (a) the free ligand H L; (b) [Cd (H L) Cl ]
2
2
2
2
complex>
<
Fig 3: Postulated conformations of the H L around the central −C(O)NHC(S)N-
2
group >
Interestingly, upon metal complexation, the spectral data of the complexes not
only proved the formation of one stable structure but also the NH's protons have not
been lost via thioenolization of C=S group and thus the sulfur atom coordinate to the
metal atoms.
1
H-NMR spectrum of the zinc complex exhibited shielded singlet signals of the
thioamide and amide NH's protons at 10.98 ppm and 10.78 ppm while other aromatic
protons resonated at 8.10-7.91 ppm (m, 2H, arom), 7.87 ppm (2d, 2H, J = 6.65, 6.90
Hz, arom), 7.53 ppm (2d, 2H, J = 8.4, 6.65 Hz, arom), 7.51-7.46 ppm (m, 1H, arom),
7
.44 ppm (2d, 2H, J = 8.6, 6.85 Hz, arom), 1.97 (s, 3H, CH ), 1.91 (s, 3H, CH ). The
3 3
appearance of the signals of acetate methyl groups were further confirmed by the IR
data.
1
H-NMR spectrum of the cadmium complex exhibited two singlet signals at 12.60
ppm, 11.59 ppm correspond to the thioamide and amide NH's protons, respectively,
while other aromatic protons resonated at 7.95 ppm (2 d, 2H, J = 7.65 Hz, arom),
1
2

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7
.71-7.76 ppm (m, 3H, arom), 7.63 ppm (2d, 2H, J = 7.65 Hz, arom), 7.51 ppm (2d,
H, J = 7.65 Hz, arom), (Fig.2).
2
In a similar manner, the mercury complex showed singlet signals at 13.06 ppm and
2.93 ppm related to the thioamide and amide NH's protons respectively, while the
1
aromatic protons appeared at 8.00 ppm (d, 2H, J = 7.65 Hz, arom), 7.90 ppm (2d, 2H,
J = 8.4, 6.8 Hz, arom), 7.85-7.80 ppm (dd, 1H, J = 7.65 Hz, arom), 7.53 ppm (dd,
1H, J = 8.4, 6.8 Hz, arom), 7.33-7.28 ppm (m, 3H, arom).
The thioamide proton signal in [Cu (HL) Cl].2H O is upfield shifted relative to its
2
2
parent ligand. This shift is attributed to the participation of the thioamide in bonding
to the copper ion, and thus further confirms the IR data. The thioamide proton signal
was observed at δ11.60. The amide proton signals displayed at δ 11.10 ppm and the
aromatic protons signals are shown at δ 7.15–8.00ꢀppm. The integration values of all
signals indicate the bonding of two ligand molecules to the copper ion, thus
confirming the micro analytical data.
Thus on the basis of the elemental analyses, molar conductance and spectral
data an octahedral geometry has been assigned to Zn (II) complex while Cd (II)
and Hg (II) complexes exhibited tetrahedral geometry. However, The Cu (I) atom is
three-coordinated by the sulfur atoms of two ligands and by one chlorine atom. This
result is similar to that found for copper complexes with N-ferrocenoyl-N’-
aryl(alkyl)thioureas , where three coordinated copper derivatives were found [49].
3.1.4. Mass spectra analysis
The electron impact mass spectrum of the ligand H L exhibited a well- defined
2
parent peak at m/z 271, with a relative intensity = 15% corresponding to
C H N SO) and consistent with formulation of H L, in addition to other
(
1
4
13
3
2
successive fragments at m/z (%): 256(4), 237(8), 150(66), 121(10), 106(100), 77(52),
9(19). Scheme 2 illustrates possible fragmentation pathways of H L.
6
2
<
Scheme 2: The possible fragmentation pathways of H L ligand >
2
1
3

ACCEPTED MANUSCRIPT
3.1.5. Thermal studies:
Thermal data of the free ligand H L and its metal complexes were studied
2
utilizing thermo gravimetric analysis (TGA), derivative thermo gravimetric analysis
DrTGA) and differential thermal analysis (DTA) methods under a nitrogen
(
atmosphere and the results are collected in table 3 and in Fig. 4. The correlation
between the different decomposition steps of the compounds with the corresponding
%
weight losses are discussed in terms of the molecular formula of the studied
compounds. Schemes 3 and 4 display representative examples of the proposed
mechanism in TGA mass losses of [Zn(H L) (OAc) ] and [Hg(H L) Cl ] complexes.
2
2
2
2
2
2
<
<
Table 3: Thermal analysis of the free ligand H L and its metal complexes>
2
Fig. 4: TGA DrTGA of (a) H L; b) [Cu (H L) Cl].2H O;
2
2
2
2
(
c) [Zn(H L) (OAc) ]; (d) [Cd (H L) Cl ] and (e) [Hg(H L) Cl ]>
2 2 2 2 2 2 2 2 2
<
Scheme 3: The proposed decomposition to TGA mass losses of
Zn(H L) (OAc) ] complex>
[
2
2
2
<
Scheme 4: The proposed decomposition to TGA mass losses of [Hg(H L) Cl ]
2 2 2
complex>
The TGA / DrTGA profile curves of the ligand H L and its metal complexes
2
(Fig .4) exhibited successive decomposition in three cumulative stages in the
temperature range 200-245 °C, 260-435 °C and 305-700 °C, respectively. From the
thermal data it is clear that while the free ligand completely decomposed, leaving a
negligible amount of carbon residue, both the copper complex [Cu(H L) Cl].2H O
2
2
2
and the cadmium complex [Cd(H L) Cl ] underwent decomposition leaving copper
2
2
2
sulfide and cadmium oxide, respectively, as remaining residues [50]. On the other
hand, mercury (II) commenced decomposition, within a total estimated mass loss of
100 % (calcd. 99.98 %), Fig 4(e) and Table 3, indicating a volatile decomposition
product as Hg vapor. Hardy, et al. [51] have reported that mercuric oxide is the
product of heating HgS and this oxide decomposes to mercury vapor and oxygen at
about 500°C. This process was also referred to reactive sublimation, where the
1
4

ACCEPTED MANUSCRIPT
decomposition of HgS has been identified to proceed according to the chemical
reaction [52]:
HgS(S) →Hg (g) + 1/2 S (g)
2
Calculations of thermodynamic parameters
The thermodynamic parameters of decomposition processes of the organic
ligand and its metal complexes, namely, activation energy Ea*, enthalpy (∆H*),
entropy (∆S*) were evaluated by employing the Horowitz-Metzger equation [53],
(Table 4). The order of chemical reactions (n) was calculated via the peak symmetry
method by Kissinger [54]. The asymmetry of the peak, S, is calculated as follows:
2
S = 0.63n ------------------------------------------------------------------------------ (1)
1
/2
n =1.26 (a/b) ------------------------------------------------------------------------- (2)
The value of the decomposed substance fraction, αm, at the moment of
maximum development of reaction (with T = T ) being determined from the relation
m
(3) [53].
1
/1-n
(
1-α ) = n
-------------------------------------------------------------------------- (3)
m
The values of collision factor, Z, can be obtained in case of Horowitz Metzger
by making the use of the relation (4) [53]:
2
Z= (Ea* / RT ) φ exp (Ea*/ RT ) = KT /h exp (∆ S*/R) --------------------- (4)
m
m
m
-1
where, R represents molar gas constant, φ rate of heating (K s ), ∆S* the
entropies of activation, K the Boltzmann constant, and h the Planck’s constant [53],.
The change in enthalpy (∆H*) for any phase transformation [55] taking place at any
peak temperature, Tm, can be given by the following equation: ∆S* = ∆H*/Tm.
Based on least square calculations, the Ln ∆T versus 1000 / T plots for all
complexes, for each DTA curve, gave straight lines from which the activation
energies were calculated according to the reported methods [55]. The slope is of
Arrhenius type and equals –Ea*/R.
1
5

ACCEPTED MANUSCRIPT
<
Table 4: Kinetic parameters of free organic ligand H L and its metal
2
complexes>
According to the data obtained from DTA curves, the following remarks can be
pointed out:
i-
The calculated values of the collision number, Z, for the H L showed a direct
2
relation to Ea*. The maximum and minimum Z values are 2.02 and 13.64,
respectively, suggesting different degradation mechanisms with variable
speeds.
ii- The activation energy of the complexes is expected to increase with decreasing
metal ion radius [56]. The smaller size of metal ions permits a closer approach
of the ligand. The trend in the calculated Ea*, values using Horowitz-Metzger
method was also observed for [Cd(H L) (Cl) ] and Hg(H L) (Cl) ] complexes
2
2
2
2
2
2
at the first stage of decomposition (473K), where the following order was
observed:
−1
Ea* for [Cd (H L) (Cl) ] = 360.60 kJmol > Ea* [Hg(H L) (Cl) ] = 174.61
2
2
2
2
2
2
−1
kJmol which is in accordance with r Cd(II) =103 pm < r Hg(II) =112 pm
57].
[
iii- The calculated values of the collision number Z for zinc and cadmium
complexes, showed a direct relation to Ea*, indicating that theses complexes
undergo nearly similar mechanism of degradation, (elimination of 2C H ).
6
6
However, this relation was not observed for copper and mercury complexes
indicating that the latter complexes undergo different degradation mechanisms
with variable speeds.
iv- The values of the decomposed substance fraction, α , Table (4) at the
m
maximum development of the reaction are of nearly the same magnitude and
lie within the range 0.483 – 0.632. The maximum and the minimum T values
m
are 893 K and 473 K, respectively.
v- The change of entropy, ∆S* values for the ligand and its metal complexes, are
-1
-1
nearly of the same magnitude within the range (-0.230 to -0.248) JK mol
1
6

ACCEPTED MANUSCRIPT
indicating that the transition states are more ordered, thus in a less random
molecular configuration than the reacting complexes [58].
vi- The appearance of the fractional orders Table (4) suggests that the reaction
proceeds via complicated mechanisms [59].
vii- The negative values of ∆H* mean that the decomposition processes are
exothermic.
3.2. Antimicrobial activity
In the light of interesting antimicrobial activities of the coordination
complexes, the ligand, H L and its metal complexes were screened against
2
pathogenic bacteria strains Staphylococcus aureus, Bacillus subtilis and Micrococcus
luteus (Gram-positive bacteria), Escherichia coli, Pseudomonas aeruginosa and
Proteus vulgaris (Gram-negative bacteria) and Candida albicans (yeast). Tetracycline
and Streptomycin served as standard bacteriocides and Amphotericin B was used as
standard fungicide. Screening results are summarized in table 5 and shown in Fig 5.
The bacterial screening results revealed that the tested free ligand exhibited
pronounced activity against Bacillus subtillis and Micrococcus luteus strains with a
growth inhibition zone diameter (25 mm and 19 mm, respectively) greater than the
standard bactericides in use, Streptomycin.
The inhibition values observed for the prepared organic ligand was also higher than
those found in metal complexes. This observation is comparable to those obtained
when using Ni (II) complexes of ethyl ester morpholine thiourea derivatives and
thiourea derivatives of α-amino acids [60]. The ligand may be more reactive with the
microelements present in the medium or the formed complexes may have an
uncommon coordination that may be inert to cell constituents. Along with this
explanation, we can conclude that the prepared ligand may be more reactive with the
microelements necessary for bacterial nutrition.
<
Fig. 5: Antimicrobial screening results of H L ligand and its metal complexes >
2
1
7

ACCEPTED MANUSCRIPT
<
Table 5: Antimicrobial screening results of H L ligand and its metal
2
complexes>
The ligand H L was found to be inactive against Proteus vulgaris (Gram-negative
2
bacteria), however, its complexes exhibited notable activity. Such increased activity
of the metal chelates can be explained on the basis of Overtone’s concept and
chelation theory [61]. According to overtone’s concept of cell permeability the lipid
membrane that surrounds the cell favors the passage of only lipid soluble materials,
due to which liposolubility is an important factor that controls antimicrobial activity.
On complexation, the bounded metals may block the enzymatic activity of the cell or
else metals may catalyze toxic reactions among cellular constituents [62] [Thus, it
may be said that the complexation of H L with studied metal ions gives the sensitive
2
nature of the ligand against some bacteria.
Inhibiting the growth of Bacillus subtilis bacteria by mercury complex is
higher than those by other prepared metal complexes. Copper complex showed no
activity against gram negative bacteria Escherichia coli and Pseudomonas aeruginosa
even over a longer time. On the other hand, zinc complex is inactive against Bacillus
subtilis and Pseudomonas aeruginosa bacteria. The variation in the activity of
different complexes against various organisms depends either on the impermeability
of the cells of the microbes or differences in ribosome in microbial cells [26].Finally,
neither H L nor its metal complexes exhibited anti- Candida albicans activity.
2
3
. 3. Characterization of Hypodentate Ligating Resin
The new hypodentate coordinating resin [PS-SO -H L]was synthesized based on the
2
2
modification of Amberlite XAD -16 using chlorosulfonic acid and the hypodentate
ligand H L.The elemental analyses of chlorosulphonated polystyrene, PS-SO Cl and
2
2
the ligating resin [PS-SO -H L] are included in table 6. From the data presented, it is
2
2
possible to calculate the first step of modification of Amberlite XAD-16 to the
chlorosulphonatedAmberlite (Scheme 5), which delivers the product with about 4
mmol of sulphonyl groups per gram. It was reported [63,64] that the use of a
hydrophilic chlorosulphonyl group as the anchoring linkage for the synthesis of
1
8

ACCEPTED MANUSCRIPT
various supported ligands gives significant advantage over the more widely used
chloromethyl group with emphasis on high capacity and decreased toxicity in the
studies of polymer pendant ligands. Transformation of PS-SO Cl to the new
2
hypodentate ligating resin was confirmed based on nitrogen analysis Table (6) which
agree with the structure of [PS-SO -H L] and
EDS analysis (Fig.6) from the
2
2
disappearance of the Cl peak. Furthermore, the IR spectrum of the ligating resin
-1
displayed ʋ(NH) and ʋ(C=S) bands at 3465, and1277 cm respectively, in addition
-1
to the thioamide bands at 1575, 1400, 1160 and 845cm .The morphology of PS-
SO Cl and the new resin [PS-SO -H L] is shown in Fig.7.
2
2
2
<
<
<
Table 6: Elemental analysis of the ligating resin and its metal complexes>
Scheme 5: Synthesis of hypodentate ligating resin PS-SO -H L>
2
2
Fig. 6: EDS analysis of (a) [PS-SO Cl]; (b) [PS-SO -H L]>
2
2
2
<
Fig. 7: The SEM photographs of PS-SO Cl (top image) and [PS-SO -H L]
2 2 2
(bottom image). >
3
.3.1. Metal complexes of hypodentate ligating resin PS-SO -H L
2
2
The hypodentate ligating resin PS-SO -H L reacted with Cu (II), Cd (II) and Ag (I)
2
2
ions to yield the corresponding metal complexes. These complexes were
investigated by elemental analyses using atomic absorption technique, EDS and FT-
IR spectroscopy. All the complexes are insoluble in most common solvents and it is
impossible to perform molar conductivity measurements. Table 6 lists the analytical
data of metal complexes of the hypodentate ligating resin PS-SO -H L.
2
2
EDS analysis of the prepared metal complexes of hypodentate ligating resin PS-SO2-
H2L (Fig. 8) showed the characteristic peaks of the examined metals and thus
supported the complex formation or absorption of these metal ions on the surface of
the resin.
<
Fig. 8: EDS analysis of (a) [Cu (Ps-SO -H L) (NO )]; (b) [Ag (PS-SO -
2 2 2 3 2 2
H L) (NO ) ]; (c) [Cd (Ps-SO -H L) (SO )]>
2
2
3 2
2
2
2
4
1
9

ACCEPTED MANUSCRIPT
The FT-IR spectra of the resin complexes (Fig. 9) display a red shift of ʋ(C=S)
-1
-1
appearing at 1260 -1255 cm compared to 1277 cm in the free resin, confirming the
coordination of the resin to the metal ion through the sulphur atom of C=S group.
The participation of the thioamide S atom was further confirmed by the shift in
-1
thioamide bands from 1575, 1400, 1160 and 845 cm in the free resin to 1565-
-1
1576,1423- 1442,
1153-1150 and 731
cm in the resin complexes.The
metallopolymer complexes [Ag2 (PS-SO -H L) (NO ) ] and [Cu (PS-SO -
2
2
2
3 2
2
-1
H L) (NO )]exhibit new bands at 1499 and 1269 cm for the Ag-resin and at 1478
2
2
3
-1
-1
and 1231 cm for the Cu-resin and with ꢁʋ = 230 and 247 cm respectively. These
new bands assigned to ʋ (NO ) and ꢁʋ values indicate monodentate nitrato group
a
2
[
65]. However [Cd (PS-SO -H L) (SO )] complex, displayed new bands at 1214,
2 2 2 4
-1
8
40 and 643 cm which assigned to chelating bidentate sulphato group [65]. Thus
based on these data the nitrato- and sulphato- groups are bonded to the metal ion
and/or adsorbed on the resin surface to neutralize the positive charge(s) on the metal
ion. Thus metal ions are coordinated to the resin surface rather than physically
adsorbed.
<
Fig. 9: FT-IR spectra of (a) [Ps-SO -H L], (b) [Cu (Ps-SO -H L) (NO )],
2
2
2
2
2
3
(
c) [Ag (PS-SO -H L) (NO ) ], (d) [Cd (Ps-SO -H L) (SO )] >
2
2
2
2
3 2
2
2
2
4
3
.3.2. Metal uptake efficiency of PS-SO -H L
2
2
The effect of pH on the sorption capacity of the ligating resin PS-SO H L, toward
2
-
2
Cu (II), Ag (I) and Cd (II) has been studied in Table 7 and shown in Fig. 10. From
the given results it is clear that the maximum adsorption for these metal ions
-1
occurred at pH 6.0 with an adsorption amount of 4.3, 4.0 and 3.7 mmolg for Cu (II),
Cd (II) and Ag (I) and, respectively. Thus the data demonstrated the high adsorption
efficiency of PS-SO -H L toward Cu (II) ion and the difference in the maximum
2
2
capacity indicates the ease of separation of copper ions from a mixture of Cu (II), Cd
II), and Ag (I) ions. The acidity of the medium can affect the metal ion uptake by
(
the resin. At low pH value the high concentration of hydrogen ion may compete
with the metal ions for bonding to the active sites on the surface of the adsorbent thus
2
0

ACCEPTED MANUSCRIPT
preventing the adsorption of metal ions onto the resin. Whereas at pH> 7.00, the
three metal ions may precipitate out as metal hydroxides which leads to an increase
in metal uptake [63, 66].The detailed studies concerning other factors affecting the
metal uptake by the new PS-SO -H L resin, such as time, temperature, foreign ions
2
2
as well as the determination of thermodynamic parameters and kinetic properties of
the removal process are ongoing and will be published in a future paper.
<
<
Table 7: The effect of pH on the metal sorption of [PS-SO -H L] >
2
2
Fig. 10: Effect of pH on the metal sorption of [PS-SO -H L] >
2
2
Conclusion
The nanosized hypodentate ligand, N-Benzoyl-N'-(p-amino phenyl) thiourea, was
synthesized by nanoprecipitation method. Direct reactions with CuCl •2H O, Zn
2
2
(
CH CO ) •2H O, CdCl •2H O and HgCl furnished the corresponding complexes in
3 2 2 2 2 2 2
good yields. Analytical studies revealed that the free ligand H L acts as hypodentate
2
in nature and bonded to the metal ion via the sulfur atom forming mononuclear non-
electrolyte diamagnetic metal complexes. The Cu (II) was reduced to Cu (I) during
the coordination process with oxidation of the ligand. Thermal studies demonstrated
the volatilization of the mercury complex, the degradation of copper and cadmium
complexes producing copper sulfide and cadmium oxide residues, respectively, and
the formation highly stable zinc complex. To achieve a better pharmacological
profile, in vitro antimicrobial activity was screened against different bacteria strains
and Candida albicans (yeast). The ligand performed high antibacterial activity
against certain bacterial strain compared to its complexes, and the standard
bacteriocide in use. The ligand was successfully immobilized on modified Amberlite
XAD-16 resin to investigate its metal uptake capacity in aqueous solution. The new
resin was characterized and the extent of metal adsorption reached maximum at pH
2
+
2+
6.0 for Cu (II), Cd (II) and Ag (I) respectively in the following order: Cu
Cd
+
Ag . These results render nanosized N-benzoyl-N'-(amino phenyl) thiourea H L
2
particularly as attractive antibacterial agent and promising adsorbent.
2
1

ACCEPTED MANUSCRIPT
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6
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[
61] P. Vijayan, C. Raghu, G. Ashok, S. A. Dhanaraj, B. Suresh, Indian J. Med.
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[
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827–1839 and references there in.
5
[
1
[
[
64] A. Elassar, A. El-Dissouky, B.J.A. Jeragh, A.Bu-Olian, S. Rizk,J. Chem. Eng.
Data 55 (2010) 4830–4839 and references there in.
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Compounds, Wiley, New York, 1978.
[
66] H. S. Lin, L. S. Lai, G. H. Leu, J. Hazard. Mater. 76 (2006) 139–153.
2
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ACCEPTED MANUSCRIPT
Figure Captions
Figure 1: SEM image of the free nanosized ligand H L.
2
1
Figure 2: Hnmr spectra of: (a) the free ligand H L (b) [Cd (H L) Cl ] complex.
2
2
2
2
Figure 3: Postulated conformations of the H L around the central −C(O)NHC(S)N-
2
group.
Figure 4: TGA DrTGA of (a) H L; (b) [Cu (H L) Cl].2H O;
2
2
2
2
(
c) [Zn (H L) (OAc) ]; (d) [Cd (H L) Cl ] and (e) [Hg (H L) Cl ].
2 2 2 2 2 2 2 2 2
Figure 5: Antimicrobial screening results of H L ligand and its metal complexes.
2
Figure 6: EDS analysis of (a) [PS-SO Cl ] and (b) [PS-SO -H L].
2
2
2
Figure 7: The SEM photographs of PS-SO Cl (top image) and [PS-SO -H L]
2
2
2
(bottom image).
Figure 8: EDS analysis of (a) [Cu (Ps-SO -H L) (NO )]; (b) [Ag (PS-SO -
2
2
2
3
2
2
H L) (NO ) ]; (c) [Cd (Ps-SO -H L) (SO )]
2
2
3 2
2
2
2
4
Figure 9: FT-IR spectra of (a) [Ps-SO -H L], (b) [Cu (Ps-SO -H L) (NO )]
,
2
2
2
2
2
3
(
c) [Ag (PS-SO -H L) (NO ) ], (d) [Cd (Ps-SO -H L) (SO )].
2
2
2
2
3 2
2
2
2
4
Figure 10: Effect of pH on the metal sorption of [PS-SO -H L].
2
2
2
7

ACCEPTED MANUSCRIPT
Element Analysis Calc.
Molar
Yield
%)
Melting
point (◦C)
(
Found)
(
Conductance
Compound
Formula
Color
-1
-1
-1
%C
%H
%N
%S
%M
(ꢀ cm mol )
6
2.0
62.1)
7.2
(47.5)
2.9
53.4)
6.3
46.6)
1.3
41.7)
4.8
15.5
11.8
7
8
233
---
H2L
C H N SO
Yellow
---
14
13
3
(
(4.5)
4.2
(15.7)
11.8
(11.6)
8.9
4
8.9
(8.5)
9.0
Yellowish
green
70
>300
>300
>300
>300
[
[
[
[
Cu (H L) Cl].2H O
CuC H N S O Cl
1.6
1.7
2.0
2.9
2
2
2
28 30
6
2
4
(3.4)
4.4
(11.5)
11.6
(8.6)
8.8
5
5
8
6
0
0
0
Zn (H L) (OAc) ]
ZnC H N S O
6
White
White
Cream
2
2
2
32 32
6
2
(
(
(
(3.7)
3.6
(11.4)
11.6
(8.7)
8.8
(9.1)
15.5
(15.9)
4
Cd (H L) Cl ]
CdC H N S O Cl
28 26 6 2 2 2
2
2
2
(3.2)
3.2
(11.3)
10.3
(8.5)
7.9
4
---
Hg (H L) Cl ]
HgC H N S O Cl
28 26 6 2 2 2
2
2
2
(2.6)
(10.4)
(7.6)
Table 1: Elemental analysis and physical data of H L and its metal complexes
2