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In the present work, we studied the role of an anionic surfactant, sodium dodecyl sulfate, and a cationic surfactant,
dodecyltrimethylammonium chloride, in the sorption of 4,4′-distyrylbiphenyl sodium sulfonate (Tinopal CBS) onto
modified cellulose fibers. Fluorescence spectroscopy was used to quantify the amount of sorbed Tinopal CBS on the
fiber surface. Differences in the spectral properties and the efficiency of sorption of the whitener/surfactant/fiber
system are explained in terms of electrostatic interactions. Our results also show that the sorption efficiency is greater
for solutions containing cationic surfactants only below the critical micelle concentration, while anionic surfactants
show a smooth influence on the sorption process.
those determined by plotting the vibronic ratio I1/I3 of the pyrene Figure 4. Ratio of the vibronic band intensities I1/I3 of the pyrene
fluorescence spectrum ([Py] ) 5.0 × 10-7 mol L-1) versus fluorescence spectrum versus the concentration of (a) DTAC and
surfactant concentrations in aqueous solutions, where I1 and I3 (b) SDS. [Py] ) 5.0 × 10-7 mol L-1. For I1 λem ) 372 nm, for I3
are intensities of the pyrene bands at 373 and 384 nm, respectively. λem ) 384 nm, and λexc ) 334 nm.
Using a sigmoid fit, the cmc of DTAC is 19.6 mmol L-1 (Figure
4a), and that of SDS is 7.0 mmol L-1 (Figure 4b), which are in
agreement with the literature (20.0 and 7.0 mmol L-1,
respectively).49-51
According to the spectral differences of the Tinopal emission
in aqueous solutions due to the surfactants, we conclude that
with SDS (anionic surfactant), where the spectra are similar to
those of the aqueous solutions, the interaction surfactant/Tinopal
is repulsive and Tinopal remains in the aqueous solution or, at
most, at the micelle/water interface (Figure 5a). On the other
hand, the spectrum and, consequently, the interaction Tinopal/
DTAC (cationic surfactant) are similar to those of the layer-
by-layer system, and Tinopal is similarly sorbed onto the viscose
surface. Tinopal molecules preferentially interact with the micelle
surface, which is positively charged (Figure 5b). Therefore, the
electrostatic surfactant/Tinopal interaction plays an important
role in Tinopal distribution in micellar aqueous solutions.
Figure 6 shows the excitation (λem ) 430 nm) and emission
(λexc ) 348 nm) spectra of Tinopal CBS sorbed onto viscose Figure 5. Model for the structure of micelles with Tinopal
fibers for several sorption intervals. As can be seen, the emission distribution in aqueous solutions with SDS (a) and DTAC (b)
surfactants.
spectrum is composed of well-resolved vibronic bands centered
at λem ) 415 nm and at λem ) 438 nm with a shoulder at the
red edge, similar to our observation of the emission spectrum of DTAC (Figure 3b). We attribute the higher energy to the 0-0
layer-by-layer films46 as well as the aqueous solution containing band and the lower energy band to the vibronic 0-1 progression.
As previous discussed, this result is explained by the confinement
(49) Rosen, M. J. Surfactants and Interfacial Phenomena, 2nd ed.; John Wiley of the Tinopal CBS molecules within cavities of the fiber surfaces,
& Sons: New York, 1989. producing a quasi-linear (shaper) emission spectrum. It is well-
(50) Tadros, F. Surfactants; Academic Press: London, 1984.
(51) Kalyanasundaram, K.; Thomas, J. K. J. Am. Chem. Soc. 1977, 99, 2039- known that greater spectral resolution can be observed for
2044. fluorophores in solutions or in solid matrixes when the cages
9870 Langmuir, Vol. 22, No. 24, 2006 Iamazaki and AtVars
surfactant type (cationic or anionic). Nevertheless, the Tinopal/ system with SDS although there is a charge inversion form
cationic and Tinopal/anionic surfactant interactions are distinct, negative to positive when the SDS concentration is increased
and the fluorescence spectrum can be a fingerprint of such distinct from 1 to 12 mM. Furthermore, a greater amount of Tinopal is
interactions. From the fluorescence emission profile we conclude sorbed in the presence of DTAC solutions where the ζ-potential
that there is a partition of Tinopal between the micelles and the is negative. Understanding these data requires further systematic
aqueous phase in micellar solutions and for cationic micelles studies.
Tinopal is preferentially located within the micelles. The
fluorescence spectrum of Tinopal in confined environments shows Acknowledgment. We thank FAPESP, CNPq, CAPES, and
greater vibronic resolution, either in micellar solution or in the MCT/CNPq/IMMP for financial support and fellowships. We
solid state (sorbed onto fibers and in layer-by-layer films). also thank Professor Carol Collins for useful discussions.
The role of surfactant in the sorption process depends on several
Supporting Information Available: Table 1, concentrations
parameters, including the charge of the surfactant molecules and of Tinopal in aqueous solutions and the weight by weight ratio of Tinopal
surfactant concentration. Surfactant also interacts with the fiber sorbed onto fibers (mass by mass) as a function of time (10 mL of
surface, increasing the interface concentration of surfactant that aqueous Tinopal solution with a concentration of 5.8 × 10-6 mol L-1
undergoes phase separation. Quantitative analysis of the Tinopal and constant temperature); Table 2, concentrations of Tinopal in aqueous
sorption onto the surface of viscose fibers shows that the anionic solutions and the weight by weight ratio between Tinopal sorbed onto
surfactant has almost no influence while the cationic surfactant fibers (mass by mass) in the presence of SDS (dipping time timmersion )
20 min, 10 mL of Tinopal at a concentration of 5.8 × 10-6 mol L-1 and
plays an important role in the sorption only below its cmc. This constant temperature); Table 3, concentrations of Tinopal in aqueous
is a consequence of the relative strength of interactions between solutions and the weight by weight ratio of Tinopal sorbed onto fibers
surfactant micelles and Tinopal and between Tinopal and the (mass by mass) in the presence of DTAC (dipping time timmersion ) 20
fibers. min, 10 mL of Tinopal at a concentration of 5.8 × 10-6 mol L-1 and
It is noteworthy that there is no apparent correlation between constant temperature); and Figure 1, electron scanning micrograph of
the efficiency of the sorption process and the ζ-potential a fiber surface. This material is available free of charge via the Internet
at http://pubs.acs.org.
determined for every system. We have observed that the amount
of Tinopal sorbed per gram of fiber is almost constant in the LA061309K