Synthesis, Optical and Surface Properties of the New Gemini
Quaternary Ammonium Surfactants Containing DSD Acid-
triazine Structure
Maosheng Wana, Jinzhao Chena, Xinchun Shena, and
Chengbo Caoa,*
aSchool of Chemistry and Chemical Engineering,
Shandong University
Jinan, Shandong, 250100, China
Jinglan Guob
bBiology Institute of Shandong Academy of Sciences
Jinan, Shandong, 250014, China
Abstract—Four novel gemini quaternary ammonium surfactants containing DSD acid-triazine structure were synthesized using
a facile three-step synthetic route , from 4,4'-diamino-2,2'-disulfonic-stilbene (DSD acid), cyanuric chloride and dimethyl
dodecylamine. The structures and optical properties of compounds (6a-d) were characterized by Fourier-Transform infrared (FT-
IR) spectroscopy, UV-visible absorption spectra and fluorescence emission spectrum. The surface tension and the Critical Micelle
Concentration (CMC) were evaluated. The result shows that the four compounds at lower concentrations can greatly reduce the
surface tension of aqueous solutions. The spectroscopic properties of these quaternary ammonium salts are assessed for their
effectiveness and potential as fluorescent brightening agents.
Keywords-Quaternary ammonium, Surfactants, DSD acid, Critical micelle concentration
1. Introduction
Quaternary ammonium compounds (QACs) as surfactants
[1-2] and antibacterial activity [3-6] are widely used in dyestuff,
textile, medicine Industry and scientific research. Particularly,
those owning two quaternary ammonium nitrogen atoms called
gemini surfactants, seem to exhibit more effective
antimicrobial activities. Because of the greater propensity to
form micelles and the further efficient decrease of surface
tension compared with the single-chain surfactant
corresponding conventional counterparts, gemini surfactants
were attracting growing attention. As well, DSD acid-triazine
structure compounds (called fluorescent brightening agents)
absorb light in the near ultraviolet region of the spectrum and
emit the light of violet-blue fluorescence in the visible region
(430-440 nm) [7-8], which were widely used for whitening
textile, paper and biological staining [9].
In this paper, we have reported the full details of syntheses
of gemini surfactants with long chain quaternary ammonium
group on triazine moiety. The newly synthesized compounds
were prepared from DSD acid, cyanuric chloride and dimethyl
dodecylamine in 3 steps with 80-85% overall yield. The
structures and optical properties of obtained compounds were
characterized. In addition, the surface tension and the Critical
Micelle Concentration (CMC) of the four compounds (6a-d)
were evaluated.
2. Experimental
A.Synthesis of compound 3
The synthetic course is shown in Scheme 1. Characterization
data as shown in Table. 1. Cyanuric chloride (1) (18.4 g,
0.1mol) was added to the mixture solution of dimethyl
dodecylamine (2) (21.3 g, 0.1mol) in water (1000 mL) at 0Υ.
After the addition was completed, the reaction mixture was
adjusted with 10% sodium hydroxide to maintain pH 5 and
stirred for 2.5 h at 0-5Υ. Then the precipitate was filtered and
dried to obtain compound 3 in 95% yield.
C
HC H
SO
3
H
HO
3
S
NH
2
H
2
N
N
N
N
Cl
Cl
Cl N
CH
3
H
3
C C
12
H
25
N
N
N
Cl
Cl
N
CH
3
CH
3
C
12
H
25
Cl
C
HC H
SO
3
H
HO
3
S
H
N
H
NNN
N N
NN
N
Cl
Cl
N
H
3
CC
12
H
25
CH
3
Cl
C
12
H
25
H
3
C
H
3
CCl
+
12
3
4
5
6
+
(i)
C
HC H
SO
3
H
HO
3
S
H
N
H
NNN
N N
NN
N
OR
RO
N
H
3
CC
12
H
25
CH
3
Cl
C
12
H
25
H
3
C
H
3
C
Cl
(ii)
(iii)
Scheme 1. Synthesis of compounds
Open Journal of Applied Sciences
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Reagents and conditions: (i) H2O, 0-5ć, 2.5 h; (ii) NaOH, H2O, 40-45ć, 4 h,
then HCl aq; (iii) a. NaOH, H2O, 100ć, 5 h b. RX, 100ć, 5 h, then rt, HCl
aq.
B.Synthesis of compound 5
Compound (3) (15.9 g, 40 mmol) was added a solution of
DSD acid (4) (7.4 g, 20 mmol) and NaOH (1.6 g, 40 mmol) in
water (400 mL) at the room tempreture. After the addition was
completed, the reaction mixture was warmed to 40-45 Υ and
stirred for 4 h. The reaction mixture was transferred to a beaker
and acidified to pH 5 with 4 M HCl solution. The precipitate
was filtered and dried to obtain compound 5 in 96% yield.
C.Synthesis of compounds 6a-d
NaOH (0.21 g, 5.2 mmol) was added a solution of compound
5 (2.84 g, 2.6 mmol) in water (150 mL). The reaction mixture
was stired and warmed to 100 Υ for 5 h. Halohydrocarbon (5.2
mmol) was added to the reaction mixture at 100 Υ for 5 h. The
reaction mixture was transferred to a beaker and acidified to
pH 6 with 4 M HCl solution. The precipitate was filtered and
dried to obtain compounds (6a-d) in 80-85% overall yield.
TABLE 1. CHARACTERIZATION DATA OF THE COMPOUNDS
3. Results and discussion
D.UV/visible absorption and Fluorescence measurements
Steady-state fluorescence spectra were recorded on a Perkin
Elmer, L50 spectrofluorimeter instrument. All experiments
were carried out using freshly prepared solutions containing
2×10-2 g/L of the compounds (6a-d) in deionized water and
adjusting solution to pH 9 with NaOH aq, using a 10 mm
quartz cuvette. As shown in Fig. 1, compounds (6a-d) have
characteristic absorptions in the range of 300 ~ 400 nm. The
emitting fluorescence of compounds (6a-d) locate in the range
of 400 ~ 500 nm as shown in Fig. 2.
250 300 350 400 450
0. 0
0. 1
0. 2
0. 3
Absorbance
Wavelength (nm)
6a
250 300 350 400 450
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
Absorbance
Wavelength (nm)
6b
250 300 350 400 450
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
Wavelength (nm)
Absorbance
6c
250 300 350 400 450
0. 0
0. 1
0. 2
0. 3
0. 4
0. 5
0. 6
Absorbance
Wavelength (nm)
6d
Fig. 1. UV/visible absorption spectra of compounds (6a-d)
From the Fig.1, we can know that there are one isomer in
the ultraviolet region, each has its maximum absorption. The
four compounds in aqueous solution have trans-isomer
maximum absorption wavelength at 326 ~ 344 nm and a cis-
isomer has not been found.
350 400 450 500 550 600
0
50
100
150
200
250
300
350
Fluorescence
Wavelength (nm)
6a
Identify applicable sponsor/s here. (sponsors)
Entry RYield (%)IR (KBr, cm–1)
6a
CH
3
CH
2 81 3498, 3212, 1702
6b
PhCH
2 85 3424, 3212, 1702
6c
CH2=CHC H2
84 3484, 3209, 1701
6d
CH
2
80 3426, 3212, 1702
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350 400 450 500 550 600
0
50
100
150
200
250
Fluorescence
Wavelength (nm)
6b
350 400 450 500 550 600
0
50
100
150
200
250
300
Fluorescence
Wavelength (nm)
6c
350 400 450 500 550 600
0
50
100
150
200
250
Wavelength (nm)
Fluorescence
6d
Fig.2. Fluorescence emission spectra of compounds 6a-d
From the Fig.2, The four compounds in aqueous solution
emit fluorescence in the 370 ~ 540 nm, the most intense
between the 433 ~ 450 nm. Because of the common structure,
the products have the similar shape of fluorescence emission
spectra curve. the products have the similar shape of
fluorescence emission spectra curve.
UV/visible absorption and fluorescence emission maxima of
the compounds as shown in Table. 2. From the Fig.1 and Fig.2,
the compounds (6a-d) can be used as fluorescent brightening
agents.
TABLE 2. ABSORPTION AND FLUORESCENCE DATA OF THE COMPOUNDS
E.Surface tension measurements
        
surfactants (6a-d) were measured by the Du Nouy ring method
at 303 K. The surface tension was measured three times for
each sample with a 40 minute interval to ensure that the data
was equilibrium between each reading. The critical micelle
concentration (CMC) values were determined using a series of
aqueous solutions of the surfactants at various concentrations,
and estimated from the break point of each surface tension
versus concentration on curves. The values of surface tension
decrease continuously critical micelle concentration (CMC)
values were determined using a series of aqueous solutions of
the surfactants at various concentrations, and estimated from
the break point of each surface tension versus concentration on
curves. The values of surface tension decrease continuously
and then become almost constant along a wide concentration
range as shown in Fig. 3.
1E-51.5E-52E-5 2.5E-53E-5
50
52
54
56
58
60
C (mol/L)
J mN/m
6a
1E-5 1E-4
36
38
40
42
44
J mN/m
C(mol/L)
6b
4.5E-5 6E-5
46
47
48
49
50
51
52
C (mol/L)
J mN/m
6c
9E-61.8E-5 2.7E-53.6E-5
46
48
50
52
54
56
J mN/m
C (mol/L)
6d
Fig. 3. Variation in the surface tension with the concentration for 6a-d
Compound 6a6b6c6d
abs (nm) 383 344 326 327
fl (nm) 443 443 445 437
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The ability of the surfactants to lower surface tension at the

shown in Table 3. The instrument was calibrated against
double distilled water at the time of measurement.
TABLE 3. TCMC VALUES OF COMPOUNDS (6A-D)
Generally surfactant refers to a class of compounds which
can greatly decrease the surface tension in lower concentration
aqueous solution compared with other solutes. With
experimental detection, these four compounds called surfactant
of quaternary ammonium salt showed remarkable ability to
reduce the surface tension in the low concentration aqueous
solution. The surface tension and surface activity of surfactant
were considered and proved to be related to many factors such
as the kind of compensation ion, electrostatic interaction,
electrostatic shielding effect, the countra-ion combination,
temperature and other element. Among the four compounds we
synthetized, that their countra-ions are all chloridion, however
with the different substituent groups attaching the parent
       
val           
the compound whose substituent group is benzene ring is the
minimum as well as that the one whose substituent group is
double bond or epoxy compound is the maximum. The
existence of benzene ring who is non-polar group gives rise to
the sparse arrangement in the water surface of the surfactant,
and changes the ability of interfacial adsorption which is
attributed to the strong hydrophobic role between benzene
rings. Therefore, this has the lower surface activity compared
with other higher ones. But among the four compounds, this
has the highest surface activity as the strongest ability of
reducing the surface tension of the aqueous solution. Both the
two types of compounds with epoxide group and double bond

electrostatic shielding effect, the similar countra-ion
combination, the minor difference of the ion volume, the nearly
equal ability of interfacial adsorption and the similar degree of
difficulty to form micelle of the two, which is consistent with
the test results. Consequently, this type of compound is a
growing in hydrophobic material researching.
4. Conclusions
Through a simple three-step condensation reaction, we
obtained the four new gemini quaternary ammonium
surfactants containing DSD acid-triazine structure with high
yields. The obtained compounds were characterized by UV-
visible absorption spectra, fluorescence emission spectra and
IR spectroscopy. The surface tension and the Critical Micelle
Concentration (CMC) were investigated. The result showed
that the compounds (6a-d) have better optical performance as
fluorescent brightening agents and can greatly reduce the
surface tension of aqueous solutions at lower concentration as
new gemini surfactants.
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Compound 6a6b6c6d
 (mN m-1) 50.93 36.47 46.30 46.50
CMC (mol L-3) 2.6×10-5 9.0×10-5 6.3×10-5 3.63×1 0-5
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