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Preparation of Novel Cationic Surfactants From Epichlorohydrin: Their Surface Properties and Biological Activities

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J Surfact Deterg (2010) 13:159–163

DOI 10.1007/s11743-009-1141-7

ORIGINAL ARTICLE

Preparation of Novel Cationic Surfactants from Epichlorohydrin:


their Surface Properties and Biological Activities
A. S. Mohamed Æ M. Z. Mohamed

Received: 3 September 2008 / Accepted: 23 May 2009 / Published online: 25 June 2009
Ó AOCS 2009

Abstract A novel series of mono-quaternary ammonium Because of the predominantly negatively charged nature
salts was prepared by the reaction of fatty esters of meth- of natural colloids and surfaces, cationic surfactants form
yldiethanolamine with epichlorohydrin in the presence of strong adsorption layers and hydrophobize the surfaces of
amine hydrochloride. The ease of the reaction with epi- these materials. Applications of cationic surfactants include
chlorohydrin was found to be due to the assistance of softeners, cosmetic products, electron-coatings, and the
amine hydrochloride in opening the epoxide ring and to stabilization of adhesive polymer latexes as well as in
neighboring-group participation by the hydroxyl group of mining and paper manufacturing [8].
the mono-ammonium salt in the quaternization step. The
surface properties of the prepared compounds and their
biological activities were measured. The prepared com-
Experimental
pounds had good water solubility and showed characteristic
surface active properties.
Synthesis of Fatty Esters of Methyldiethanolamine
Keywords Quaternary ammonium salts 
Methyldiethanolamine (0.1 mol, 11.9 g) (Aldrich) was
Epichlorohydrin  Surface properties  Biological activities
esterified by lauric, palmitic, or stearic acid (0.1 mol; 20,
25.6, or 28.4 g, respectively) (Sigma, St. Louis), in toluene
under an inert atmosphere (N2 gas) using p-toluene sulfonic
Introduction
acid (0.001 mol) as a catalyst. After the complete removal
of the produced water (0.1 mol, 1.8 ml), the reaction
Conventional single chain surfactant molecules consist of
mixture was dissolved in petroleum ether (60–80 °C) in a
hydrophobic and hydrophilic parts. With increasing con-
separating funnel to remove the catalyst used. The solvents
centrations, they form micelles and then lyotropic meso-
were removed using a rotary evaporator under reduced
phases. Surfactants molecules above the critical micelle
pressure [9.] The products were designated as (1a–c) and
concentration (CMC) in aqueous solution are known to
had the general formula R1R2R3N. The groups R1, R2 and
form a variety of microstructures such as spherical, ellip-
R3 are located in Scheme 1.
soidal, vesicular, rod-like and thread-like forms [1–4]. The
microstructure of surfactant aggregates depends on the
molecular structure of the surfactants and solution condi- Synthesis of Fatty Esters of Methyldiethanolamine
tions, such as concentration and temperature [5–7]. Hydrochloride

This compound was best prepared by the neutralization of


methyldiethanolamine laurate, palmitate, or stearate with
A. S. Mohamed (&)  M. Z. Mohamed
hydrochloric acid and then stirred until the precipitation
Petrochemicals Department,
Egyptian Petroleum Research Institute, Cairo, Egypt stopped. The precipitate was filtered, and then recrystal-
e-mail: ammona_salem@hotmail.com lized by ethyl alcohol [10]. The products were designated

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160 J Surfact Deterg (2010) 13:159–163

Scheme 1 Reaction of fatty


esters of methyl
diethanolamine, its
hydrochloride, and
epichlorohydrin

Ia Ib Ic
R1 CH3 CH3 CH3
R2 C2H4OH C2H4OH C2H4OH
R3 (CH2)2 O–CO(CH2)10CH3 (CH2)2 O–CO(CH2)14CH3 (CH2)2 O–CO(CH2)16CH3
Yield (%) 82 89 92

as (2a–c) and had the general formula R1R2R3NHCl. The Table 2 FTIR characterization for the prepared compounds
groups R1, R2, and R3 are shown in Scheme 1. Functional group Wave no (cm-1)

Reaction of Fatty Esters of Methyldiethanolamine Ia Ib Ic


with Epichlorohydrin –OH 3388.87 3385.24 3389.43
–CH2 2935.23 2937.42 2936.32
A mixture of methyldiethanolamine laurate, palmitate, or –CH3 2848.16 2850.02 2850.83
stearate (8 mmol; 2.4, 2.85, or 3.1 g respectively), their –N ?
2504.03 2511.74 2509.62
hydrochlorides (4 mmol; 1.35, 1.57, or 1.68 g, respec- –C=O 1738.14 1735.42 1735.15
tively), epichlorohydrin (4 mmol, 0.37 g) (Merck-Schuc- –C–O 1173.35 1175.11 1174.20
hardt), and ethanol (5 ml) as a solvent was stirred for 8 h at
room temperature (Table 3). Quaternary ammonium salts
(Ia,b,c) were isolated by recrystallization from acetone [11]. Table 3 Conditions of the reaction of fatty esters of methyldietha-
The quaternary ammonium salts produced were waxy. nolamine, its hydrochloride, and epichlorohydrin
They have the structures and the yields shown in Molar ratio Temp. Time Solvent
Scheme 1. Elemental analyses (Table 1), FTIR spectros-
MDEA MDEA ester. Epichlorohydrin
copy (Table 2) as well as 1H-NMR spectroscopy were ester HCl
performed to ensure the purity of the prepared ammonium
salts. 2 1 1 rt 8 Ethanol
rt room temperature

Evaluation Methods of Surface Active Properties


49 Ia
Surface Tension (c) and Critical Micelle Concentration Ib
46
Ic
Surface tension (mN/m)

The relation between the surface tension and the concen- 43


tration (in term of log c) of the synthesized surfactants at
25 °C was determined and represented in Fig. 1. The CMC 40
and cCMC (surface tension at CMC) values were determined
37
from the break point of each surface tension versus
concentration. 34

31
Table 1 Elemental analyses for the prepared cationic surfactants Ia–c
28
Surfactant C% H% N% Cl%
F Calc. F Calc. F Calc. F Calc. 25
5.3 5 4.7 4.4 4.1 3.8 3.5 3.2 2.9 2.6 2.3 2
Ia 54.08 55.81 9.37 9.53 3.36 3.25 16.23 16.51 - Log (C)
Ib 58.97 59.25 9.96 10.08 2.97 2.88 14.45 14.60
Ic 60.37 60.70 10.20 10.31 2.80 2.72 13.56 13.81 Fig. 1 Variation in the surface tension of surfactants Ia–c versus
concentration at 25 °C

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J Surfact Deterg (2010) 13:159–163 161

Table 4 Surface properties of the prepared cationic surfactants at 25 °C


Q
Surfactant CMC (M/L) cCMC CMC Cmax 9 10-11 Amin DGads DGmic
(mN/m) (mN/m) (mol/cm2) (n m2) (kJ/mol) (kJ/mol)

Ia 1.8 9 10-4 30 42 1.82 9.06 -44.26 -21.36


-4
Ib 6.9 9 10 39 33 2.82 5.84 -29.64 -18.03
Ic 1.11 9 10-3 37 35 2.49 6.62 -30.81 -16.86

Q
Effectiveness ( CMC) diffusion disc method, where a sterilized disc of filter paper
Q saturated with a measured quantity of the sample is placed
The effectiveness of the surface active agent ( CMC) is on a plate containing a solid bacterial medium (nutrient
defined as the difference between the surface tension of the agar broth) or fungal medium (Dox’s medium), which has
surfactant solution at the CMC (cCMC) and that of bidis- been heavily seeded with the spore suspension of the tested
tilled water (co) at constant temperature [12]: organism. After incubation, the diameter of the clear zone
PCMC ¼ c0  cCMC : of inhibition surrounding the sample is taken as a measure
of the inhibitory power of the sample against the particular
Maximum Surface Excess Cmax test organism [15].

The maximum surface excess of the surfactant solution


(Cmax) is defined as the concentration of the surfactant Results and Discussion
molecules at the interface near the CMC [13].
1 dc
Cmax ¼  ð Þ The prepared compounds were confirmed by elemental
2:303RT dlogc T
analysis (Table 1) and FTIR (Table 2). The results were
where R = 8.314 J mol-1 K-1, T is the absolute temper- found to be compatible with the supposed structures. Also
ature and (dc/dlog c) is the slope of the c versus log c plot the 1H-NMR spectra of the synthesized compounds showed
at room temperature (Fig. 1). different bands at d = 0.96 ppm (m, –CH3); d = 1.29 ppm
(m, –CH2); d = 1.33 ppm (m, –CH2CH3); d = 1.68 ppm
Minimum Surface Area (Amin) (m, –CH2CH2COO); d = 2.25 ppm (t, –CH2COO); d =
2.0 ppm (s, –OH); d = 3.97 ppm (–CH2OH); d =
The minimum surface area Amin is the minimum area per 4.52 ppm (t, –CH2OCO); d = 3.3 ppm (s, –?N CH3);
molecule of the prepared compounds at the interface and d = 3.52(m, –CH2 N?); d = 3.65 ppm (q, –CH2Cl) and
was calculated using the following equation: d = 4.16 ppm (m, CHOH). These data of 1H-NMR spectra
Amin ¼ 1016 =Cmax N confirm the expected hydrogen proton distribution in the
synthesized cationic compounds.
where N is Avogadro’s number and Cmax is the maximum
surface excess. Surface Activity

The Standard Free Energies of Micellization DGomic Surface properties of the prepared cationic surfactants were
and adsorption DGoads measured and are summarized in Table 4. The variation in
surface tension of surfactants Ia–c versus -log molar con-
It is expected that the two processes of adsorption and centration (-log c) is shown in Fig. 1. This figure shows
micellization occur simultaneously. The dominance of the two characteristic regions. At lower concentrations, the
two processes is decided by the free energy changes. variation of surface tension is very significant, whereas at
Hence, the free energies of adsorption (DGads) and micel- higher concentrations, it is relatively weak. The intercept of
lization (DGmic) were calculated according to Rosen’s these two regions indicates the CMC. From the curves,
methodology [14] several surface parameter and energetic factor values could
Q
DGmic ¼ 2:303RTlogðCMCÞ be extracted including CMC, CMC, Cmax, Amin, DGmic,
DGads ¼ DGmic  ð0:6023Pcmc Amin Þ: and DGads [16] which are listed in Table 4.

Measurement of Antimicrobial Activity Critical Micelle Concentration and cCMC

The synthesized surfactants were screened for their anti- It is clearly evident from Fig. 1 that the surface tension
microbial activity against bacteria and fungi using the decreases as the concentration increases, where the

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162 J Surfact Deterg (2010) 13:159–163

surfactant molecules are adsorbed on the liquid/air interface The maximum surface excess of the surfactant solution
of the solution until the surface of the solution is completely showed the number of surfactant molecules located in unit
occupied, and then the excess molecules tend to self aggre- area at the air/water interface. That ability is enhanced by
gate in the bulk forming micelles. There are two antagonistic increasing the hydrophobic character of these molecules.
effects controlling the micellization, the hydrophobic group Values of Cmax represented in Table 4 show that
which is an important driving force in micellization and the increasing the hydrophobic character of the prepared
hydrophilic group which opposes micellization. In our compounds causes a corresponding increase in the Cmax
investigation, since the hydrophilic group is constant, we value. This indicates that the molecules are more tightly
observe that the CMC values of the prepared compounds packed in the water/air interface for longer alkyl chain
decrease as the length of the alkyl chain increases. The CMC surfactants [18]. This is true for compounds Ia, Ib but
value for the compound Ic is relatively high since it is a bulky compound Ic deviates again.
molecule which deviates from this trend.
The surface tension values at the respective CMCs Minimum Surface Area (Amin)
(cCMC) are given in Table 4. The results reveal that an
increase from Ia to Ic in the hydrophobic chain length Increasing Cmax indicates a larger number of adsorbed
makes the surfactant less surface active. molecules at the air/water interface. Hence, the area
available for each molecule at the interface will decrease. It
Q
Effectiveness ( CMC) is obvious from the data of Amin in Table 4 that increasing
the alkyl chain length decreases the area occupied by each
The surface tension (c) values at the CMC are used to molecule.
calculate values of the surface pressure effectiveness as
mentioned before. The effectiveness of adsorption is an Standard Free Energies of Micellization and Adsorption
important factor for foaming, wetting and emulsification, (DGmic DGads)
since tightly packed coherent interfacial films have very
different interfacial properties than loosely packed, non- From Table 4 values of DGmic, DGads are always negative
coherent films [17]. The most efficient surfactant results in indicating that these two processes are spontaneous; how-
a greater lowering of surface tension at CMC. From values ever, there is a greater increase in the negative values of
Q
of CMC listed in Table 4, it is observed that compound Ib DGads compared to those of micellization. This suggests a
achieved the maximum reduction of the surface tension at tendency of the molecules to be adsorbed at the interface
its CMC value. rather than micellization in the bulk of the solution.

Maximum Surface Excess (Cmax) Antimicrobial Activity

A substance that lowers the surface energy is thus present One of the most important applications of surfactant series
in excess at or near the surface, i.e., when the surface which have high tendency towards adsorption is their use
tension decreases with increasing activity of surfactant, C as antibacterial and antifungal agents. The role of these
is positive. compounds can be summarized as increasing the

Table 5 Antimicrobial activity of the synthesized cationic surfactants


Sample Inhibition zone diameter (mm/mg sample)
Bacillus Escherichia Staphylococcus Streptococcus Candida albicans
subtilis (G?) coli (G-) aureus (G?) faecalis (G?) (Fungus)

Water 0.0 0.0 0.0 0.0 0.0


Tetracycline (ref1) 30 34 32 31 37
Amphotricine (ref2) 0.0 0.0 0.0 0.0 0.0
Ia 13 15 13 14 15
Ib 0.0 0.0 0.0 0.0 16
Ic 0.0 0.0 0.0 0.0 0.0
Compound [14 mm, significant activity
7–13 mm, moderate activity
\7 mm, weak activity [22]

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J Surfact Deterg (2010) 13:159–163 163

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3. Zana R, Benrroau M, Rueff R (1991) Alkanediyl-.alpha.,omega.-
bis (dimethylalkylammonium bromide) surfactants. 1. Effect of
A. S. Mohamed was born in Egypt (1965) and received her B.Sc. and
the spacer chain length on the critical micelle concentration and
M.Sc. from the Suez Canal University and her Ph.D. from Ain Shams
micelle ionization degree. Langmuir 7:1072–1075
University (2000). She is presently Assistant Professor of Applied
4. Zana R, Talmon Y (1993) Dependence of aggregate morphology
Surfactants in the Petrochemicals Department (Egyptian Petroleum
on structure of dimeric surfactants. Nature 362:228–230
Research Institute, EPRI). Her interests are focused on the synthesis
5. Vinson PK, Bellare JR, Davis HT, Miller WG, Scriven LE (1991)
and evaluations of surfactants in several fields including, biocidal
Direct imaging of surfactant micelles, vesicles, disks, and ripple
application, solubilization, and antitumor activity.
phase structures by cryo-transmission electron microscopy.
J Colloid Interface Sci 142:74–91
6. Hirata H, Sato M, Sakaiguchi Y, Katsube Y (1988) Small angle M. Z. Mohamed was born in Egypt (1963) and received her B.Sc.,
X-ray scattering study of an extremely elongated micelle system M.Sc. and her Ph.D. from Ain Shams University (1997). She is
of CTAB-p-toluidine solution. Colloid Polym Sci 266:862–864 presently Assistant Professor of Applied Surfactants in the Petro-
7. Jaeger DA, Li B, Clark T Jr (1996) Cleavable double-chain chemicals Department (Egyptian Petroleum Research Institute,
surfactants with one cationic and one anionic head group that EPRI). Her interests are focused on the synthesis and evaluations of
form vesicles. Langmuir 12:4314–4316 surfactants in several fields including, biocidal application, solubili-
8. Shukla D, Tyagi VK (2006) Cationic gemini surfactants: a zation, and antitumor activity.
review. J Oleo Sci 55:381–390
9. Negm NA, Mohamed AS (2004) Surface and thermodynamic
properties of diquaternary bola-form amphiphiles containing an
aromatic spacer. J Surf Deterg 7:23–30

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