Petroleum-dispersing and antimicrobial activity of newly synthesized polymeric surfactants tethering tetrachlorophthalimide moiety

Article abstract of DOI:10.1007/s13738-020-02023-9

The development of compounds with dual or multi-functions or activities is being paid attention in the scientific community. Herein, two series of phthalimide-containing copolymers were synthesized and structurally characterized and their potency against selected microbial strains was evaluated. Our study mainly focused on evaluating both the antimicrobial and surface activities of new corresponding polymeric cationic surfactants for removing petroleum thin films with their increased dispersing capacity. The synthesis process includes the formation of N-methacryloyloxytetrachlorophthalimide monomer, homopolymerization, and exchange reactions with various amino- and hydroxy-compounds for the synthesis of copolymers. Lastly, polymeric surfactants were obtained via the quaternization of some copolymers with dimethyl sulfate. Among the tested derivatives, compounds 5a, 5b, 6c, 6d, and 7b showed higher activities than the standard drugs which reached 2.45-fold (44?mm against A. niger) in copolymer 5b. Besides, the three polymeric surfactants displayed strong surface activity features including Krafft point, foaming, and emulsifying power. Moreover, polymeric surfactant 7b exhibited strong dispersion behavior for petroleum in both undiluted form (K_d from 91.60 to 93.20%, τ = 30–96?h) and diluted form (K_d from 95.7 to 98.1%, τ = 5–96?h).

Full text of DOI:10.1007/s13738-020-02023-9

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-020-02023-9
ORIGINAL PAPER
Petroleum‑dispersing and antimicrobial activity of newly synthesized
polymeric surfactants tethering tetrachlorophthalimide moiety
Hany I. Mohamed1,2 · Mahmoud Z. Basyouni1,3 · Ahmed A. Khalil · Kaouser A. Hebash · Ahmed H. Tantawy
1
1
1,2,3
Received: 10 June 2020 / Accepted: 29 July 2020
©
Iranian Chemical Society 2020
Abstract
The development of compounds with dual or multi-functions or activities is being paid attention in the scientiꢀc commu-
nity. Herein, two series of phthalimide-containing copolymers were synthesized and structurally characterized and their
potency against selected microbial strains was evaluated. Our study mainly focused on evaluating both the antimicrobial
and surface activities of new corresponding polymeric cationic surfactants for removing petroleum thin ꢀlms with their
increased dispersing capacity. The synthesis process includes the formation of N-methacryloyloxytetrachlorophthalimide
monomer, homopolymerization, and exchange reactions with various amino- and hydroxy-compounds for the synthesis of
copolymers. Lastly, polymeric surfactants were obtained via the quaternization of some copolymers with dimethyl sulfate.
Among the tested derivatives, compounds 5a, 5b, 6c, 6d, and 7b showed higher activities than the standard drugs which
reached 2.45-fold (44 mm against A. niger) in copolymer 5b. Besides, the three polymeric surfactants displayed strong sur-
face activity features including Kraꢁt point, foaming, and emulsifying power. Moreover, polymeric surfactant 7b exhibited
strong dispersion behavior for petroleum in both undiluted form (K from 91.60 to 93.20%, τ=30–96 h) and diluted form
d
(
K from 95.7 to 98.1%, τ=5–96 h).
d
Keywords Copolymers · Polymeric surfactants · Antimicrobial activity · Petroleum-dispersing · Surface activity
Introduction
conditions via either conventional or microwave-assisted
reactions [1]. As applicable materials, NHTHPs in blend
with 1,4-diamino-2,3-dichloroanthraquinone (DADCAQ)
were used as catalysts to facilitate the aerobic oxidation of
alkyl arenes [2].
Phthalimide derivatives, especially N-hydroxytetrahaloph-
thalimides (NHTHPs), have been paid attention in recent
years due to their wide range of valuable applications.
Their synthetic procedures include condensation of substi-
tuted phthalic anhydrides with hydroxylamine in alkaline
In a novel one-step process, N-hydroxytetrachlorophthal-
imide (NHTCP) was utilized as a mediator for the electro-
chemical oxidation of allylic C–H bond on large scale. This
operation exhibits high chemoselectivity, wide substrate
extension, besides its eꢁortlessness (Scheme 1) [3]. Cata-
lytically, a donor–acceptor complex of N-acyloxyphthalim-
ide and Hantzsch ester (HE) was used for the metal-free
Hany I. Mohamed and Mahmoud Z. Basyouni these authors are
equally contributed.
Electronic supplementary material The online version of this
article (https://doi.org/10.1007/s13738-020-02023-9) contains
supplementary material, which is available to authorized users.
3
C(sp )−H allylation via aryl carboxyl radicals in a regio- and
chemoselective reaction [4].
For energy purposes and as an anolyte, N-methyl-
phthalimide was employed for all-organic redox ꢂow bat-
tery (AORFB) by electrochemical measurements in which
*
Ahmed H. Tantawy
ahmed.tantawy@mail.hzau.edu.cn
1
2
3
Department of Chemistry, Faculty of Science, Benha
University, Benha 13518, Egypt
2
,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) was used as
catholyte [5].
Department of Chemistry, College of Science, Huazhong
Agricultural University, Wuhan 430070, Hubei, China
In the polymers field, many studies for some homopol-
ymers and copolymers which incorporate reactive phthal-
imide group were reported [6–11]. Decorating polyimides
College of Plant Science and Technology, Huazhong
Agricultural University, Wuhan 430070, Hubei, China
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
O
Materials and experimental procedures
-
1
1
0 mA mmol , NHTCP
R
R
tBuOOH, pyridine, acetone
(
)n
(
)n
Materials
Tetrachlorophthalic anhydride, methacrylic acid, N,N′-
Scheme 1 NHTCP-mediated scalable electrochemical allylic C–H
dicyclohexylcarbodiimide (DCC), and benzoyl peroxide
oxidation
(
BP) were supplied by Sigma-Aldrich (St. Louis, USA)
and used without further puriꢀcation. Hydroxylamine
hydrochloride, N,N-dimethylethanolamine, N,N-dime-
thyl-1,3-propanediamine, 2-aminopyridine, 2-aminothia-
zole, salicylic acid, methyl 4-aminobenzoate, p-anisidine,
phenol, benzyl alcohol, dimethyl sulfate (DMS), methyl-
ene chloride, methanol, dimethylformamide (DMF), and
diethyl ether were provided by Al-Nasr chemical com-
pany (Cairo, Egypt). Infrared spectra were measured on
with some rigid phthalimide groups as chain-branch
enhances their resistance for friction and heating stabil-
ity without affecting their optical properties and solubility
[
12]. From this point of view, a high cell voltage (2.0 V)
in a polymer-based AORFB system was constructed via
introducing a phthalimide-loaded redox-active copolymer,
a TEMPO-loaded polymer as cathode-active material and
separator (a porous membrane) [13].
1
a Thermo-Scientiꢀc Nicolet iS10 FTIR spectrometer. H
NMR spectra were generated on JNM-ECA II 500 MHz
Physical combination of polymers and surfactants may
lead to improvements in the thermal conductivity proper-
ties and performance of polymer-coated composites [14].
However, polymeric surfactants (PS, chemical hybrids
of polymers and surfactants) combine the advantages of
both components [15]. Some PS were developed to be
used under harsh reservoir conditions through enhancing
temperature stability, aqueous solubility, low adsorption,
and foaming characteristics which make them suitable
for reservoirs with elevated temperature and increased
salinity [16], and other bio-based PS molecules have mul-
tiple pH-responsiveness [17]. Recent studies report their
applications as efficient breakers for the asphaltic crude
oil emulsion [18] or as petroleum thin-film removers from
the water surface [19–28]. Besides, some alginates poly-
meric cationic surfactants exhibited good antimicrobial
activities as well as high corrosion inhibition efficiency
FT NMR JEOL system in DMSO-d or CDCl and tetra-
6
3
methylsilane (TMS) as an internal standard. Spectra of
energy-dispersive X-ray (EDX) were measured using EDX
JSM 5400, National Research Centre (Cairo, Egypt).
Experimental procedures
Synthesis of N‑hydroxytetrachlorophthalimide (NHTCP, 2)
A mixture of tetrachlorophthalic anhydride (2.86 g,
1
2
0 mmol) and hydroxylamine hydrochloride (1.39 g,
0 mmol, 2.0 equiv.) in pyridine (10 mL) was introduced
into a round-bottom ꢂask ꢀxed within a reꢂux system.
After reꢂuxing for 4 h at 130 °C, the crude NHTCP was
obtained by pouring the cold mixture on conc. HCl/
crushed ice (pH = 2−3) followed by vacuum ꢀltration.
The product was recrystallized from ethanol to give 2.28 g
[
29].
Dispersants are used to break up oil slicks during oil
(
80%) of pure 2 with a melting point of 213–215 °C.
spill response efforts and limit floating oil from impact-
ing sensitive ecosystems. There is a huge quantity of these
chemicals annually at the water’s surface and below the
surface to combat oil. Their mechanism of action, the
effect on marine animals, and other quality-determining
features have been reported [30–34].
Synthesis of N‑methacryloyloxytetrachlorophthalimide
NMATCP, 3)
(
To a solution of NHTCP (2, 3.01 g, 10 mmol) in dry
Herein, we report on the synthesis and characterization
of tetrachlorophthalimide-incorporating copolymers and
polymeric cationic surfactants. The current study focuses
on the evaluation of antimicrobial activity for all prepared
derivatives and the surface activity as well as the capac-
ity in dispersing petroleum thin films for polymeric sur-
factants. Our work opens the doors for the development of
polymeric materials, especially surfactants with excellent
water solubility, for dual application as antimicrobials and
surface-active agents.
methylene chloride (30 mL), methacrylic acid (0.86 g,
1
0 mmol) was added and the mixture was cooled in ice-
bath to (0–5 °C). As one portion, DCC (2.06 g, 1.0 equiv.)
was added followed by stirring at room temperature for
2
0 h. The formed N,N′-dicyclohexylurea (DCU) was elimi-
nated through ꢀltration, and the ꢀltrate was evaporated
to dryness in vacou. A mixture of benzene/methylene
chloride (20/80) was used for puriꢀcation of the solid
residue via recrystallization to aꢁord 2.10 g (70%), m.
−
1
p. 142–144 °C. IR (υ, cm ): 2928 and 2852 (symm. &
1
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Journal of the Iranian Chemical Society
Table 1 1H NMR spectral data with exchange yield percent for copol-
ymers 5b–5e and 6b–6d
asymm. C-H stretching of CH /CH ), 1733 (C=O stretch-
2
3
ing of phthalimide moiety) and 1625 (olefinic C=C
1
stretching). H NMR (CDCl , δ, ppm): 2.11 (s, 3H, CH )
3
3
Compd. No.
Segment
Chemical shift δ
Yield %
and 5.97 (s, 1H, oleꢀnic)., 6.50 (s, 1H, oleꢀnic) (Figure
(ppm)
S1).
5
5
5
b
CH , CH ,
2.71, 2.86,
6.51–7.84,
11.02
2.71, 2.86,
6.98–7.93,
11.92
14
3
2
C H N,
5
4
NH
Synthesis of poly
c
CH , CH ,
97.5
54
3
2
(N‑methacryloyloxytetrachlorophthalimide) (4)
C H NS,
3
2
NH
In a polymerization tube, a 10% solution of NMATCP in
dioxane was treated eꢃciently with recrystallized benzoyl
peroxide (1.0 mol%). The tube was ꢂushed with nitrogen and
placed for 6 h in a water bath at 65 °C. After cooling, the
reaction mixture was portion wisely added to an excess of
methanol, forming the crude polymer as yellow precipitate
which was ꢀltered. The homopolymer was dissolved in a lit-
tle acetone and reprecipitated with petroleum ether to aꢁord
pure 4 with good yield (70%).
d
CH , CH ,
3.60, 3.70,
3.81,
3
2
OCH3,
C H ,
NH
6.49–8.50,
10.82
6
4
5
6
e
CH , CH ,
2.74, 2.90,
3.73,
6.55–8.16,
11.11
1.20, 3.09,
6.78–7.76,
10.19
27
3
2
CH O,
3
C H ,
6
4
NH
b
CH , CH ,
99.9
3
2
C H ,
6
4
Exchange reactions of polymer 4 with amines: synthesis
of copolymers 5a–5e
COOH
6c
CH3, CH2,
C H
CH3, CH2,
CH2O,
1.17, 3.04,
6.45–7.51
1.12, 2.89,
3.69,
25
95
6
5
The prepared homopolymer of N-methacryloyloxytetra-
chlorophthalimide (NMATCP) was subjected to react with
amino compounds. The homopolymer was dissolved in
DMF to form a 10% solution, and two equivalents of amine
were added. The mixture was agitated for 6 h at 60 °C and
then poured into diethyl ether. The copolymer was ꢀltered,
dissolved in DMF, and reprecipitated with diethyl ether.
6d
C6H5
7.34–7.37
Table 2 EDX spectroscopy data showing elemental composition for
the copolymers 5a and 6a
Element
Atomic %
Net Int.
Exchange reactions of polymer 4 with hydroxylated
compounds: synthesis of copolymers 6a–6d
5
a
6a
5a
6a
12.32
14.52
C
O
Cl
65.37
27.95
6.68
63.81
24.37
11.82
73.77
23.68
2.55
As described above for amino compounds, the homopolymer
139.89
4
was reacted similarly with hydroxy-compounds. The reac-
tion was catalyzed with two equivalents of triethylamine.
The reaction was stopped after 6 h, and the products were
puriꢀed as mentioned before. The chemical structures of
Measurements
1
the prepared copolymers are well characterized by H NMR
Critical micelle concentration
spectroscopy (Table 1 and Figures S3–S9).
Quaternization of copolymers: synthesis of polymeric
surfactants 7a–7c
(a) Surface tension
Tensiometer-K6 processor (KrÜss. GmbH, Germany) was
used to evaluate the surface tension of the target polymeric
surfactants’ solutions. Each measured sample was repeated
for three times at 298°K and determined from the average
of them, whereas the surface tension value of demineralized
water was adjusted to 72.0 mN/m at 298°K and the uncer-
tainty did not override± 0.1 mN/m.
The polymeric surfactants were obtained by heating copol-
ymers 5a, 5c, or 6a with excess DMS under free-solvent
conditions. The reaction was preserved at 95 °C for 48 h
with continuous stirring. The products 7a–7c were washed
several times with diethyl ether, and the isolated yields were
8
0–85%.
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Journal of the Iranian Chemical Society
(
b) Electrical conductivity
and Escherichia coli) and two fungal strains (Aspergillus
niger and Rhizopus oryzae).
The electrical conductivity values for surfactant solu-
Two highly common antimicrobial agents, Tetracy-
cline and Amphotericin B, were used to serve as positive
controls. The eꢁect of polymeric compounds on living
microorganisms, whether to kill or inhibit their growth,
was measured through the agar disk diꢁusion technique
tions were determined at 298°K via “model Type AD3000;
EC/TDS and Temperature meter” (Shanghai, China). The
recorded values were repeated three times for all prepared
solutions.
[
36]. Filter paper disks of 6 mm diameter were immersed
Kraꢀt point
in the solution of the tested compound (1.0 mg/mL) and
placed on the surface of the agar. Agar plates were previ-
ously inoculated with a standard inoculum size of microor-
ganisms. The Petri dishes with bacterial strains were taken
to incubate for 24 h at 35–37 °C, while those of fungal
strains were incubated for 48 h at 25–27 °C. The zones
of growth inhibition were measured which represent the
antimicrobial activities of compounds.
Via visual observations, the Kraꢁt points for the three sur-
factants’ solutions were determined. The concentrations of
solutions were at least two equivalents than the CMC of the
investigated surfactants.
Foaming power
In a 250-mL graduated cylinder, 100 mL of the surfactant
solution (0.1% (wt./v)) was added. The cylinder was stop-
pered and shaken vigorously at room temperature for 20 s.
The initial foam height represents the foaming ability, while
the foam stability was estimated by recording the time
required to reduce the foam to half of its initial value [35].
A minimum of four replicate determinations was introduced
for each sample solution.
Results and discussion
Synthesis
The main homopolymer, poly N-methacryloyloxytetra-
chlorophthalimide (4), was synthesized by a three-step
reaction. Firstly, the hydroxylamine nitrogen replaced the
cyclic ester oxygen of tetrachlorophthalic anhydride (1)
via condensation. Then, the hydroxyl group of product 2
was subjected to form an ester with methacrylic acid and
the reaction was catalyzed by DCC. Thirdly, the monomer
3 was polymerized in DMF using BP for the initiation
(Scheme 2).
Emulsifying stability
The stability of the emulsion was determined via shaking
vigorously a mixture of 10 mL (0.1% w/v) of the sample
solution with 10 mL of paraꢃnic oil at 298°K for 10 s. The
required time for separating surfactant solution (8 mL) from
the emulsiꢀcation system at a steady-state was represented
as the emulsion stability [35]. Four replicates of the experi-
ment were performed.
The ꢀrst series of copolymers (5a–5e) was synthesized
via exchanging the reactive tetrachlorophthalimidoxy
(TCPO) group in the polymer 4 with diꢁerent amino com-
pounds. Thus, it was subjected to react with N,N-dimethyl-
1,3-diaminopropane, 2-aminopyridine, 2-aminothiazole,
p-anisidine, and methyl 4-aminobenzoate (Scheme 3).
The second copolymers’ series (6a–6d) was synthe-
sized through the displacement of the TCPO group under
Petroleum‑dispersing evaluation
The petro-dispersing capacities of the polymeric surfactants
(
in both pure state and 5 wt% aq. solution) have been deter-
mined on the surface of three water of various mineraliza-
tion degrees via the Red sea crude oil from the oil ꢀelds in
the South Sinai (Egypt). For this purpose, both un-thinned
polymeric surfactant and its 5% wt. aqueous solution were
utilized. The studies were done according to the known pro-
cedure [27].
Et N-catalyzed reaction with some hydroxyl group-con-
3
taining compounds, namely N,N-dimethylethanolamine,
salicylic acid, phenol and benzyl alcohol (Scheme 4).
1
Both EDX spectra (Table 2 and Figure S2) and H NMR
spectra (Table 1 and Figures S3–S9) were utilized to calcu-
late the yields of the exchange reactions. The yield of the
copolymer 5a is 98%, while that of copolymer 6a is 90%.
Copolymers 5a, 5c, and 6a in which their structures
incorporate tertiary nitrogen atoms were quaternized with
dimethyl sulfate (DMS) under solvent-free conditions to give
polymeric cationic surfactants 7a–7c according to Scheme 5,
which represents the quaternization process and the prepara-
tion of polymeric surfactants.
Antimicrobial activity
All synthesized polymeric compounds were evaluated as
antimicrobial agents (in vitro) against various microbes
comprising bacteria and fungi. The tested microbial patho-
gens include two bacterial strains (Staphylococcus aureus
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Journal of the Iranian Chemical Society
Cl
Cl
CH
2
Cl
Cl
Cl
O
O
O
O
O
CH
2
HO C
C
2
Cl
Cl
Cl
Cl
Cl
Cl
pyridine
30°C
CH
3
O
+
NH OH.HCl
N
OH
N
CH3
2
1
DCU
DCC
O
Cl
1
O
O
3
2
CH3
H
2
C
Cl
Cl
O
O
CH2
CH3
n
Cl
O
O
O
BP / 65°C
DMF
n
N
O
N
O
Cl
O
3
Cl
Cl
Cl
Cl
4
Scheme 2 Synthetic route for poly(N-methacryloyloxytetrachlorophthalimide)
Scheme 3 Synthesis of copoly-
CH3
C
CH3
C
mers 5a–5e via exchange reac-
tions of 4 with various primary
amines
CH3
C
DMF
H C
CH2
2
x
y
H C
+
R-NH2
2
n
6
0 o
C
C
O
C
O
C
O
O
O
N
HN
N
O
O
O
R
O
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
b;
5a-5e
4
N
R = a;
c;
N
N
S
d; MeO
e; MeO
C
2
Surface tension and micellization
drawing the surface tension (g) of obtained solutions of
targeted surfactants versus their concentrations (wt/v) at
25 °C as shown in Fig. 1.
The studying of surface activity of these polymeric sur-
factants was to evaluate their possible applications in dif-
ferent industrial ꢀelds. Whereas the increase in amphiphile
concentration leads to these properties corrupt progres-
sively from ideality and at the concentration, the mole-
cules monomers will be aggregated to form micelles; an
abrupt change is noted. So, values of CMC of synthesized
polymeric surfactants have been gotten graphically by
Also, from Fig. 2, the CMC values of the quaternary
exchangeable polymers were calculated from the values of
electrical conductivity versus the concentration (wt/v) of
the obtained compounds at 25 °C. Collectively, the CMC
values, determined via both from surface tension and elec-
trical conductivity measurements, seemed identical.
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Journal of the Iranian Chemical Society
Scheme 4 Synthesis of
CH3
C
CH3
C
copolymers 6a–6d via exchange
reactions of 4 with various
hydroxylated compounds
CH
C
3
TEA/DMF
H C
CH2
2
x
y
H C
+
R-OH
2
n
6
0 o
C
C
O
C
O
O
C
O
O
O
N
N
O
O
O
R
O
Cl
Cl
Cl
Cl
Cl
Cl
Cl
Cl
6a-6d
4
COOH
R = a;
c;
N
b;
d;
Table 3 Surface activity
parameters for the synthesized
polymeric surfactants
a
b
Compd. no.
CMC (wt/v)
CMC (wt/v)
Emulsion
Foaming properties
Foaming Foam stability
Kraꢁt
point
power (min)
(
°C)
ability (mL) (t ; min)
1
/2
7
7
7
a
b
c
0.038
0.120
0.039
0.037
0.110
0.040
10± 2.2
25± 3.1
40± 3.2
70± 4.5
90± 3.0
110± 5.5
120± 3.3
135± 4.1
155± 4.8
< 0
< 0
< 0
a
CMC values obtained from surface tension measurements
CMC values obtained from conductivity measurements
b
Scheme 5 Synthesis of poly-
CH3
C
CH3
C
CH3
CH3
meric cationic surfactants 7a–7c
H C
CH2
2
H C
C
CH2
O
C
x
y
2
x
y
C
O
C
X
O
DMS
C
C
N
O
O
X
O
CH3
R3
R1
R3
N
R1
R2
R2
OSO CH3
3
5
a, 5c or 6a
7a-7c
Cl
CH
3
O
2
3
X
NR R = a; HN
N
CH
Cl
3
1
R =
N
N
c; O
N
CH
3
3
Cl
b;
O
HN
Cl
S
CH
1
3

Journal of the Iranian Chemical Society
Fig. 1 Variation of the surface tension with the concentration of polymeric surfactant (wt/v) in water at 298°K
Kraꢀt point
surfactant molecules to be situated at the interface between
diꢁerent phases. Thusly, the more molecules adsorbed at
the interface, the more impressive the emulsifying agent.
In our study, the time needed for separating 8 mL of
water from the emulsion system (0.1% surfactant solution
wt and paraꢃn oil 10 mL) was set as the emulsiꢀcation
eꢃciency. The ability of the surfactant particles to keep
the oil globule apart from each other for a longer period
is responsible for the high stability of the hydrophobic
emulsion. The results depicted in Table 3 conꢀrmed that
the synthesized surfactants can form eꢁective emulsions
with oil and therefore can be utilized for the preparation
of stable emulsions.
The solubility of cationic surfactants can be assessed
through the quantiꢀcation of Kraꢁt point values. The lower
the value of the Kraꢁt point of the prepared cationic poly-
mer, the better its solubility. The data in Table 3 showed that
all furnished polymeric surfactants exhibited Kraꢁt point
values lower than 0 °C, and this indicates that these sur-
factants have good water solubility.
Emulsifying power
Emulsifying power measures the surfactant tendency to
form both types of emulsion and reꢂects the capacity of
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Journal of the Iranian Chemical Society
Fig. 2 Variation of concentration of polymeric surfactant (wt/v) with electrical conductivity (EC, μS/cm) at 298°K
Foaming properties
petroleum-dispersing action in un-thinned surfactant,
whereas K ranges from 91.60 to 93.20%, τ=30–96 h. (in
d
Foaming indices are utilized to judge the commercial appli-
cability of novel synthesized surfactants. Such indices were
recorded for three polymeric surfactants to comprehend
the versatility of the shaped monolayer of ꢂuid surfactant
solution in the foam. The foam properties data (Table 3)
showed that all surfactants exhibited good foaming proper-
ties. Compound 7c displayed high foamability and strong
foam stability.
freshwater). Also, it exhibited a strong petroleum-dispersing
eꢁect in 5% wt. aqueous solution, whereas K ranges from
d
95.7 to 98.1%, τ=5–96 h. (in the three water of various min-
eralization degrees). Moreover, compound 7a exhibited low
petroleum-collecting in both diluted and undiluted forms,
whereas K ranges from 1.29 to 6.36, τ=0–96 h, in all used
waters. Finally, compound 7c was unstable to enhance petro-
dispersing properties.
Petroleum‑dispersing properties
Antimicrobial activity
The results of the study of petroleum-dispersing eꢁects
of generated polymeric surfactants are recorded in
Table 4. It can be noticed that compound 7b gave high
Polymeric materials with strong microbial growth inhibi-
tion eꢁect possess a vital role in many applications. When
sensitive types of equipment such as dental tools, health-care
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Journal of the Iranian Chemical Society
Table 4 Petroleum-collecting/dispersing properties of the synthesized polymeric surfactants 7a–7c
Compd. no.
Undiluted product
Distilled water
5% wt. water solution
Distilled water
Fresh water
τ (h) K (kd)
Sea water
τ (h)
Fresh water
Sea water
τ (h)
τ (h)
K (kd)
K (kd)
τ (h)
K (kd)
τ (h)
K (kd)
K (kd)
7
a
0
0
0–96
1.69
3.91
5.17
–
0
1.29
2.84
4.70
0–2
1.29
3.91
3.30
8.1
5.40
NC
0–2
1.29
4.27
5.73
–
2.90
NC
NC
NE
0–2
1.29
2.30
5.17
6.36
4.30
95.7%
96.1%
NE
0–2
1.69
2.64
3.30
–
2.00
97.8%
98.0%
NE
3
20
25–96
–
5–20
30–60
70–96
0–2
5–20
30–96
96
30
48
30
20
6
–
0–2
2
6
40–60
70–96
0–2
20–30
40–96
0–96
40–96
–
0–2
5–30
40–96
0–96
–
–
0–2
5–20
30–96
0–96
7
b
c
3.45
0–2
4.10
a
–55
0–96
NC
30–60
60–96
0–96
91.6%
93.2%
NE
NC
NC
NE
b
7
0–96
NE
a
b
NC=No Change; NE=No Eꢁect
Table 5 Antimicrobial activity (in vitro) of the synthesized polymeric
comparable values to the reference agents. By focusing on
the inhibition zones for E. coli, only four compounds exhib-
ited activity with a range between 11.3 and 29 mm com-
pared to 32 mm for Tetracycline. However, for S. aureus, the
values range from 17.3 to 26 mm compared to 28 mm for
Tetracycline. Interestingly, ꢀve compounds (5a, 5b, 5e, 6c,
and 6d) displayed high potency (>18 mm) against A. niger
with inhibition zone values higher than the reference drug
Amphotericin B. On the other hand, all compounds do not
aꢁect the fungus R. oryzae.
materials
Compd. No.
Inhibition zone diameter (IZD, mm)
Bacteria
Fungi
E. coli
S. aureus
A. niger
R. oryzae
5
5
5
5
5
6
6
6
6
7
7
7
a
b
c
d
e
a
b
c
d
a
b
c
11.3
Nil
29.0
18.3
Nil
20.0
Nil
Nil
Nil
Nil
20.0
11.6
32.0
NT
17.3
23.0
24.6
22.0
17.6
25.3
24.3
19.3
26.0
20.6
30.3
27.3
28.0
NT
24.3
44.0
9.6
9.3
18.3
5.6
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
NT
20.0
Antimicrobial activity of polymeric surfactants
21.0
28.6
34.6
24.0
21.0
17.0
By the same technique, the antimicrobial activity for the syn-
thesized polymeric surfactants 7a–7c was evaluated toward
various microbes. The values of the inhibition zone diam-
eters ranged between 11.6 and 30.3 mm (Table 5), which are
considered high values compared with the reference used.
All tested compounds exhibited good activity against the
Gram-positive bacterium S. aureus and the fungus A. niger.
Like copolymers, the three polymeric surfactants gave nega-
tive results against R. oryzae.
a
Tetracycline
NT
18.0
Amphotericin B
aNT=Not Tested
products, water puriꢀcation systems, or medical devices are
contaminated by microbes, serious issues will be developed.
To avoid microbial contamination, it is better to develop
candidates with strong activity against microbes.
Conclusions
In all scientiꢀc issues, identifying compounds with dual or
multi-functions is of great importance. One major way for
such development is the use of conjugate chemistry. The
current work describes a facile route for the synthesis of
new copolymers tethering tetrachlorophthalimide moiety.
Some of the copolymers with tertiary nitrogen atom were
converted into the corresponding polymeric surfactants via
quaternization with dimethyl sulfate. Also, the antimicrobial
activities for all polymeric materials and surface properties
including petroleum-collecting/dispersing capacities for
Antimicrobial activity of copolymers
The synthesized copolymers, with their bioactive tetrachlo-
rophthalimide group, were screened for the eꢁectiveness to
control or inhibit the growth of bacterial species as well as
fungal species.
The results presented in Table 5 indicate that the tested
compounds have strong antimicrobial activities with
1
3

Journal of the Iranian Chemical Society
surfactants have been evaluated. Compound 5b with TCPO/
pyridine conjugate displayed the highest activity against A.
niger with a value of about 2.45-fold higher than that of the
Amphotericin B. Moreover, polymeric surfactant 7b exhib-
ited very strong petroleum dispersibility in both diluted and
undiluted forms.
17. Y. Ma, J. Hao, K. Zhao, Y. Ju, J. Hu, Y. Gao, F. Du, J. Colloid
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21. Z.H. Asadov, G.A. Ahmadova, R.A. Rahimov, S.-Z.F.
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