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Langmuir 2003, 19, 2243-2248 2243

Polyelectrolyte Adsorption onto a Surface-Confined


Surfactant
Alexander B. Artyukhin, Kevin J. Burnham, Andrei A. Levchenko,
Raisa V. Talroze, and Pieter Stroeve*
Department of Chemical Engineering and Materials Science, University of California at Davis,
Davis, California 95616

Received October 1, 2002. In Final Form: December 5, 2002

Using sodium dodecyl sulfate (SDS) as a surfactant and poly(diallyldimethylammonium chloride) (PDDA)
as a polyelectrolyte, we formed a surfactant-polymer complex on a model surface of a positively charged
2-aminoethanethiol (cysteamine) self-assembled monolayer on gold. The complex formation is achieved
by first SDS adsorption on cysteamine and subsequent adsorption of PDDA on the preformed SDS layer.
Successful deposition of the PDDA layer on SDS without noticeable surfactant desorption shows that the
complex formation is a fast process. The presence of SDS-PDDA complex on a cysteamine-modified gold
substrate was observed by surface plasmon resonance (SPR) and Fourier transformed infrared spectroscopy.
The thicknesses obtained from the SPR data were 1.5 nm for SDS and 1.1 nm for PDDA. Concentrations
of SDS and PDDA in the parent solutions necessary to yield the complex upon adsorption were determined.

Introduction the polyelectrolyte on the surfactant. The deposition


should lead to surface properties that are highly noniso-
There is little understanding on the molecular level of tropic.
interactions between surface-active species and polyelec- Recent atomic force microscopy (AFM) studies3,8-18 of
trolytes at solid-liquid interfaces. Likewise, there is a soluble ionic surfactants on different surfaces show they
lack of knowledge on the self-assembly properties of do not cover surfaces in uniform monolayers. AFM images
surfactants and polymers at interfaces. Knowledge about of surfactants at the solid-liquid interface exhibit complex
these self-assembled structures is important for applica- micelle formation at surfactant concentrations above and
tions in coatings, surface cleaning, wetting, cosmetics, below the critical micelle concentration (cmc). Hemimi-
controlled release, biosensors, and biomaterials.1-4 For celles are often formed by the adsorption of charged
example, there has been considerable interest in ultrathin surfactants on uncharged surfaces. Spherical hemimicelles
molecular films made from the self-assembly of surfactants may be encountered for concentrations below the cmc,
and ionic polymers at the air-water interface.5-7 The while cylindrical hemimicelles are found at concentrations
presence of surfactants gives surface tension lowering, above the cmc. The formation of full micellar structures
and the use of ionic polymers can give rise to robust, is often found in the adsorption of charged surfactants on
ultrathin films. An area of research is the assembly of surfaces of opposite charge. Concentrations at or above
multilayers of alternating surfactants and ionic polymers the cmc can favor the formation of cylindrical micelles.3
to create semipermeable membranes for separating ions
Taking into account the complex morphology of the
and low molecular weight species. By using different types
surfaces covered by self-assembled surfactants, the latter
of surfactants and ionic polymers in the multilayer stack,
may be considered as templates to control the surface
selective membranes can be designed. Another interest is
assembly of polymer macromolecules. The key to putting
in using ionic polymers with surfactants at the solid-
to use the desirable properties of surface self-assembled
water interface for selective barrier coatings for biosensors.
surfactants lies in forming uniformly templated surfaces
It is also possible to use the self-assembly of surfactants
with a definite topology for adsorption and alignment of
on the solid-water interface to pattern the deposition of
functional macromolecules of polyelectrolytes such as
polypeptides, proteins, DNA, or synthetic polymer semi-
* To whom correspondence should be addressed. E-mail: conductors. Creating the structure in the nanometer scale
pstroeve@ucdavis.edu. Telephone: (530) 752-8778. Fax: (530) 752-
1031.
Present address: Department of Chemistry, University of (8) Liu, J. F.; Min, G.; Ducker, W. A. Langmuir 2001, 17, 4895-
4903.
California Davis, Davis, CA 95616. (9) Fleming, B. D.; Wanless, E. J. Microsc. Microanal. 2000, 6, 104-
Present address: A. V. Topchiev Institute of Petrochemical
112.
Synthesis, Russian Academy of Sciences, Moscow, Russia. (10) Liu, J. F.; Ducker, W. A. J. Phys. Chem. B 1999, 103, 8558-
(1) Goddard, E. D. In Interactions of surfactants with polymers and 8567.
proteins; Goddard, E. D., Ananthapadmanabbau, K. P., Eds.; CRC (11) Ducker, W. A.; Wanless, E. J. Langmuir 1999, 15, 160-168.
Press: Boca Raton, FL, 1993. (12) Grant, L. M.; Tiberg, F.; Ducker, W. A. J. Phys. Chem. B 1998,
(2) Uchida, M.; Kunitake, T.; Kajiyama, T. New Polym. Mater. 1994, 102, 4288-4294.
4, 199-211. (13) Lamont, R. E.; Ducker, W. A. J. Am. Chem. Soc. 1998, 120,
(3) Tiberg, F.; Brinck, J.; Grant, L. Curr. Opin. Colloid Interface Sci. 7602-7607.
1999, 4, 411-419. (14) Kiraly, Z.; Findenegg, G. H. J. Phys. Chem. B 1998, 102, 1203-
(4) Thunemann, A. F.; General, S. J. Controlled Release 2001, 75, 1211.
237-247. (15) Jaschke, M.; Butt, H. J.; Gaub, H. E.; Manne, S. Langmuir 1997,
(5) Stroeve, P.; VanOs, M.; Kunz, R.; Rabolt, J. F. Thin Solid Films 13, 1381-1384.
1996, 285, 200-203. (16) Ducker, W. A.; Wanless, E. J. Langmuir 1996, 12, 5915-5920.
(6) Stroeve, P.; Hwa, M. J. Thin Solid Films 1996, 285, 561-563. (17) Manne, S.; Gaub, H. E. Science 1995, 270, 1480-1482.
(7) Bruinsma, P. J.; Stroeve, P.; Hoffmann, C. L.; Rabolt, J. F. Thin (18) Manne, S.; Cleveland, J. P.; Gaub, H. E.; Stucky, G. D.; Hansma,
Solid Films 1996, 285, 713-717. P. K. Langmuir 1994, 10, 4409-4413.

10.1021/la026640s CCC: $25.00 2003 American Chemical Society


Published on Web 02/04/2003
2244 Langmuir, Vol. 19, No. 6, 2003 Artyukhin et al.

is important for micromanufacturing applications, such about 500 of gold was deposited on glass slides by heating the
as micro- and nanosensors, and controlled adsorption of gold target in a crucible with an electron beam at a pressure
biopolymers. below 5 10-6 Torr, with a gold deposition rate of 0.2 /s. In
The well-known process of polyelectrolyte layer-by- method 2, the slides were baked in a vacuum chamber (Edwards
AUTO 306) at 250 C for 2 h before deposition and then cooled
layer adsorption on solid-water interfaces19 is different to 30 C. Gold was then deposited in the vacuum chamber by
than the process of deposition of surfactant and poly- thermal evaporation of gold in a current-heated molybdenum
electrolytes.20-23 In the former process, the deposition boat. During gold evaporation, the vacuum was better than 3
process is started from a charged surface by sequential 10-6 Torr, the rate of deposition was 0.2-0.5 /s, and gold was
adsorption of alternatively charged polyelectrolytes, while deposited to a final thickness of 500 ( 20 which was measured
in the latter process low molecular weight surface-active by a calibrated built-in quartz crystal. The exact thickness of the
species are used instead of one of the polyelectrolytes. In gold layer prepared by both methods was determined by surface
this work, we focus on the use of sequential adsorption of plasmon resonance (SPR) spectroscopy in every experiment. Gold-
a surfactant and a polyelectrolyte on the solid-water coated slides were kept in ethanol and used within 10 days after
preparation.
interface to create self-assembled composite materials. Preparation of Thiol Monolayer. Gold-coated LaSFN9
Patterning of solid surfaces via self-assembly using glass slides were covered with cysteamine monolayer by im-
either polymers or surfactants is of recent interest,24-30 mersing them into a 5 mM cysteamine solution in ethanol for at
but patterning by sequential adsorption of a surfactant least 14 h. Slides were then rinsed thoroughly with pure ethanol
and a polymer on solid surfaces has not yet been addressed. and dried in a stream of nitrogen.
This paper deals with the first observation of sequential Measurement of SDS Surface Concentration. Since the
adsorption first of surfactant and then polyelectrolyte on change in index of refraction is linear with respect to changes
a self-assembled monolayer (SAM) of thiol on gold. The in surfactant concentration, one can use the following relation
surfactant chosen in this study, sodium dodecyl sulfate to determine the surface concentration of SDS:31,32
(SDS), is a widely used surface-active agent, and the
polymer is poly(diallyldimethylammonium chloride) d(nf - ns)
cs ) (1)
(PDDA). This polymer serves as a model, which should dn/dc
prove the whole concept and show whether the surfactant-
polyelectrolyte complex is stable at the surface and at where cs is the equilibrium excess surface concentration of SDS
what conditions. The model surface used in this work is (units of mol/m2), d is the film thickness (nm), dn/dc is the
incremental change in the refractive index of solution with an
a cysteamine (2-mercaptoethylamine) SAM on gold. increase in surfactant concentration (3.74 10-5 mM, measured
with the Abbe refractometer), nf is the index of refraction of the
Experimental Section SDS film (nf ) 1.46), and ns is the refractive index of pure solvent,
Materials. SDS was purchased from Fluka and recrystallized in our case water (ns ) 1.330).
three times from ethanol. Poly(diallyldimethylammonium chlo- Flow Cell. The flow cell was designed so that fully developed
ride), 20% aqueous solution, was obtained from Polysciences, laminar flow was achieved prior to a solution entering the SPR
Inc. Cysteamine (2-aminoethanethiol) was received from Sigma. measurement area. The cell was fabricated from Teflon with an
Water for experiments was purified by a NanoPure Diamond O-ring (Apple Rubber Products Inc.) for a seal. The flow channel
system (Barnstead) and had a resistivity of 18.2 M cm. Ethanol was 14 mm wide and 64 mm long. The gap between the glass
used for thiol solution preparation, SDS crystallization, and glass slide and the opposite Teflon wall was 0.25 mm. The SPR
slide cleaning was 200 proof (Gold Shield Chemical Co.). The measurement area was 40 mm from the inlet. The laser beam
refractive index matching fluid, sulfur in 1-iodonaphthalene, was of the SPR has a cross-sectional area of about 2 mm2. Solutions
obtained from Cargille Laboratories Inc. were pumped using a 100 mL syringe (Popper & Sons Inc.) with
Preparation of Gold-Covered Substrates. Two methods a Cole-Palmer 74900 syringe pump or a peristaltic MasterFlex
were used to deposit 99.999% gold on high-refractive-index Digistaltic 77340-00 pump (Cole-Parmer). Results were inde-
LaSFN9 glass slides (Schott, Germany) that have yielded pendent of the choice of the pump system. Connections between
considerably different results in subsequent surfactant adsorption the cell and feeding syringes and the output were made from
experiments. Prior to gold deposition in either method, glass Upchurch Scientific tubes and fittings.
slides were cleaned by sonication at 55 C first in water, then in Surface Plasmon Resonance. Formation of the SDS layer
2% Helmanex solution, and finally in ethanol, for 15 min each and subsequent PDDA adsorption were monitored by SPR. The
with thorough water rinses between sonications. In method 1, method is based on excitation of the surface plasmons by
p-polarized light at the noble metal-dielectric interface.33 Details
of the experimental procedure are described elsewhere.34,35 All
(19) Decher, G.; Hong, J. D.; Schmitt, J. Thin Solid Films 1992, 210/
211, 831. experiments were carried out at room temperature of 24 ( 1 C.
(20) McQuigg, D. W.; Kaplan, J. I.; Dubin, P. L. J. Phys. Chem. 1992, Polymer Adsorption. Poly(diallyldimethylammonim chlo-
96, 1973-1978. ride), solution in water or in 5 mM phosphate 7.0 buffer, was
(21) Li, Y. J.; Dubin, P. L.; Dautzenberg, H.; Luck, U.; Hartmann, injected into the SPR flow cell with 1 or 3 mL disposable Monoject
J.; Tuzar, Z. Macromolecules 1995, 28, 6795-6798. syringes (Sherwood Medical) after SDS adsorption had reached
(22) Kasaikin, V. A.; Litmanovich, E. A.; Zezin, A. B.; Kabanov, V. an equilibrium. A 0.1-0.5 mL air bubble was injected ahead of
A. Dokl. Akad. Nauk 1999, 367, 359-362.
(23) Litmanovich, E. A.; Kasaikin, V. A.; Zezin, A. B.; Kabanov, V. the PDDA solution in the same syringe to separate bulk SDS
A. Dokl. Phys. Chem. 2000, 373, 121-124. and PDDA solutions and prevent their mixing.
(24) Cox, J. K.; Eisenberg, A.; Lennox, R. B. Curr. Opin. Colloid Fourier Transform Infrared (FTIR) Spectroscopy of
Interface Sci. 1999, 4, 52-59. the Surface SDS-PDDA Complex. Fourier transform
(25) Jiang, X. P.; Zheng, H. P.; Gourdin, S.; Hammond, P. T. Langmuir infrared spectra were collected on a Nicolet Protege 460 setup
2002, 18, 2607-2615. equipped with a MCT detector in grazing angle reflection mode.
(26) Lee, I.; Jiang, X. P.; Zheng, H. P.; Chen, K. M.; Rubner, M. F.;
Kimerling, L. C.; Hammond, P. T. Abstr. Pap.sAm. Chem. Soc. 2001, Ten thousand scans were taken for each spectrum at 4 cm-1
221, 164-COLL.
(27) Lee, I.; Zheng, H. P.; Rubner, M. F.; Hammond, P. T. Adv. Mater. (31) Wagner, P.; Hegner, M.; Guntherodt, H. J.; Semenza, G.
2002, 14, 572-577. Langmuir 1995, 11, 3867-3875.
(28) Zheng, H. P.; Jiang, X. P.; Lee, I.; Chen, K. M.; Kimerling, L. C.; (32) Defeijter, J. A.; Benjamins, J.; Veer, F. A. Biopolymers 1978, 17,
Rubner, M. F.; Hammond, P. T. Abstr. Pap.sAm. Chem. Soc. 2001, 221, 1759-1772.
277-COLL. (33) Knoll, W. Annu. Rev. Phys. Chem. 1998, 49, 569-638.
(29) Zheng, H. P.; Rubner, M. F.; Hammond, P. T. Langmuir 2002, (34) Levchenko, A. A.; Argo, B. P.; Vidu, R.; Talroze, R. V.; Stroeve,
18, 4505-4510. P. Langmuir 2002, 18, 8464-8471.
(30) Zheng, H. P.; Lee, I.; Rubner, M. F.; Hammond, P. T. Adv. Mater. (35) Zhang, L. Q.; Longo, M. L.; Stroeve, P. Langmuir 2000, 16, 5093-
2002, 14, 569-572. 5099.
Adsorption onto a Surface-Confined Surfactant Langmuir, Vol. 19, No. 6, 2003 2245

determine the pKa values of different compounds on


surfaces, and it is generally accepted that the pKa values
are different from the bulk. To the best of our knowledge,
only one work was devoted to studying basic properties
of surface-adsorbed amines. It has been shown that the
pKa of protonated forms of 4-mercaptoaniline and 4-mer-
captopyridine SAMs on gold is higher than that in bulk37
but these compounds are considerably weaker bases than
primary aliphatic amines. From this result, we can only
conclude that pKa of protonated cysteamine on gold should
be at least 9.5 or higher.
To ensure consistency in degree of cysteamine proto-
nation, we performed a series of adsorption experiments
in 5 mM phosphate buffer at pH 7.0. Addition of the salt
decreases the cmc of the surfactant,38 and at this ionic
strength the cmc of SDS is 5.8 mM while in pure water
it is 8.1 mM.39 At SDS concentrations higher than 0.5
cmc, substitution of buffer for water has no effect on the
Figure 1. Isotherm of SDS adsorption on a cysteamine SAM amount of SDS adsorbed (Figure 1). At lower SDS
on gold. Open symbols are for evaporated gold, and closed
symbols are for e-beam-deposited gold: circles, recrystallized
concentrations, less surfactant is adsorbed in buffer than
SDS in water; triangles, uncrystallized SDS in water; squares, in water. This difference is due to the screening of
recrystallized SDS in 5 mM phosphate 7.0. Error bars are shown electrostatic interaction between SDS and cysteamine.
for experiments repeated more than one time. Lines are drawn At concentrations of SDS higher than 0.5 cmc (3-4 mM
to aid the eye: solid, e-beam-deposited gold in water; dotted, SDS), the ionic strength of the solution is primarily set
evaporated gold in water; dashed, evaporated gold in 5 mM by the surfactant itself and addition of 5 mM buffer
phosphate 7.0. increases it only 3 times. On the other hand, at 0.1 cmc
(0.6-0.8 mM SDS) 5 mM buffer brings about a 10-fold
resolution. Gold-covered LaSFN9 glass slides were used as increase in the ionic strength. Since the characteristic
substrates. The SDS layer was prepared by dipping the gold length of electrostatic interaction is inversely proportional
slide modified with cysteamine SAM into aqueous 8.1 mM SDS-
to the square root of the ionic strength, the effect is further
d25 solution for up to 1 h, and the slide was then pulled out of
the solution and dried without rinsing. Cysteamine SAM on gold enhanced at lower concentrations.
was used as a background. To obtain a surfactant/polyelectrolyte In a previous paper, we found that recrystallization of
complex on the surface, a cysteamine-modified gold-coated slide SDS was necessary and gave thinner surfactant layers on
was precoated with SDS-d25 as before and then dipped into a hydrophobic undecanethiol SAMs on gold.34 A probable
beaker with 0.2 M PDDA solution for 10 min. The PDDA solution reason for this phenomenon that has been observed by
was subsequently exchanged with pure water for seven volumes other researchers as well40 is contamination of com-
using a pump. During the rinse, the slide was always kept below mercially available SDS with dodecanol due to hydrolysis.
the water-air interface. A small amount of perhydro SDS (1 Obviously, dodecanol is more hydrophobic than SDS and
mg/mL SDS in n-butanol as the spreading solution) was spread
has a higher affinity to hydrophobic surfaces. Due to
onto the water surface in the beaker using a microliter syringe,
and the slide was then quickly removed from the solution and dodecanol adsorption at low SDS concentrations, the
dried. This procedure was found to be necessary since no complex apparent SDS coverage is higher. However, above the cmc
between SDS-d25 and the polymer was observed when the dodecanol is solubilized in SDS micelles, resulting in its
procedure was omitted. Transfer of the slide through the pure desorption, and a maximum of the adsorption isotherm
water-air interface with its high surface tension may desorb appears near the cmc. For SDS adsorption on positively
the SDS-PDDA complex on the SAM by causing the complex to charged cysteamine, we found that crystallization had no
spread on the water-air interface. For the background in this effect on the amount of SDS adsorbed (Figure 1), mainly
case, a cysteamine-modified gold substrate was immersed into because SDS has a higher affinity to cysteamine than
0.2 M PDDA solution and the subsequent procedure was the
dodecanol due to the electrostatic nature of the attraction.
same as for the sample slide. The only difference is that the
background slide was not in contact with SDS-d25 solution. This There is a difference between the two isotherms of SDS
choice of the background would compensate for IR signals arising adsorption in water presented in Figure 1. Surface
from probable surface contamination resulting from additional coverages in the two cases differ considerably. Our
treatment. All drying was performed in ambient atmosphere. previous results (filled symbols) were obtained on gold
deposited by heating a gold target by an electron beam
Results and Discussion (method 1, see Experimental Section for more details).
SDS Adsorption. We studied adsorption of anionic Subsequent experiments carried out on gold prepared by
surfactant SDS on a monolayer of positively charged thiol thermal evaporation (method 2) reproducibly yielded a
cysteamine self-assembled on gold (Figure 1). Adsorption higher surface concentration of adsorbed SDS (Figure 1).
of SDS on cysteamine is governed by electrostatic attrac- We ascribe it to the difference in gold film preparation.
tion between dodecyl sulfate anions and positively charged The gold coating obtained by method 2 was more adsorp-
ammonium headgroups of cysteamine chemisorbed on tive, with higher cysteamine coverage and subsequently
gold. Even though the exact pK of surface-confined higher surface concentrations of SDS.
cysteamine is not known, one may expect that it bears a PDDA Adsorption. A critical element in the formation
positive charge in neutral aqueous solutions. Primary of the structures under sequential adsorption of first
amines are well-known to be strong proton acceptors, and surfactant and then polyelectrolyte is the competing
the pKa value of 2-hydroxyethylammonium in bulk water
(37) Bryant, M. A.; Crooks, R. M. Langmuir 1993, 9, 385-387.
is 9.50 at 25 C.36 Significant research has been done to (38) Newbery, J. E. Colloid Polym. Sci. 1979, 257, 773-775.
(39) Clint, J. H. Surfactant aggregation; Blackie: Glasgow, 1992.
(36) CRC Handbook of chemistry and physics, 73rd ed.; Lide, D. R., (40) Turner, S. F.; Clarke, S. M.; Rennie, A. R.; Thirtle, P. N.; Cooke,
Ed.; CRC Press: Boca Raton, FL, 1992. D. J.; Li, Z. X.; Thomas, R. K. Langmuir 1999, 15, 1017-1023.
2246 Langmuir, Vol. 19, No. 6, 2003 Artyukhin et al.

Figure 3. SPR curves versus angle for the cysteamine SAM


Figure 2. Kinetics of SDS adsorption at 1 cmc on a cysteamine (solid line), SDS adsorbed on the SAM (dotted line), and PDDA
SAM on gold and following PDDA adsorption from a 0.2 M adsorbed on the SDS (dashed line).
solution on the SDS preformed layer, 5 mM phosphate buffer
7.0. Table 1. Thicknesses and Surface Concentrations of SDS
on Cysteamine/Gold and PDDA on SDS/Cysteamine/Gold
Obtained at Different SDS and PDDA Concentrations in
kinetics of surfactant desorption and polyion adsorption. 5 mM Phosphate 7.0 Buffer
To fabricate the structures, desorption of surfactant
molecules from the SAM should be slower than adsorption surface concentration
concentrations thicknesses () (mol/m2)
of the polyion covering the surfactant on the surface. In
the case of SDS adsorbed on cysteamine, desorption occurs SDS (cmc) PDDA (M) SDS PDDA SDS PDDA
within seconds upon rinsing with water or buffer.34 0.1 0.2 3 5 1.03 1.14
Another problem that might complicate interpretation of 0.2 0.2 5 7 1.71 1.6
experimental results is formation of soluble or insoluble 1 0.2 17 11 5.82 2.51
SDS-PDDA complex in bulk. To separate bulk SDS and 1.72 0.2 20 16 6.84 3.65
0.5 0.05 19 3 6.50 0.69
PDDA solutions, an air bubble was injected ahead of the 1 0.05 20 5 6.84 1.14
PDDA solution in the SPR cell. As a result, SDS and PDDA 1.72 0.05 16 3 5.48 0.69
were never in contact in the bulk. To check that the
injection of a 0.1-0.5 mL air bubble does not disturb the neous increase in reflectivity upon PDDA injection and-
preformed SDS layer on the surface, the bubble was decrease upon buffer rinse (Figure 2) are due to the
introduced into SDS solution flushing through the cell, significantly higher refractive index of 0.2 M PDDA
that is, the solutions ahead of and behind the bubble were solution (1.339) compared to water or diluted buffer
the same. SPR measurement showed that the reflectivity (1.332). The net change in reflectivity after buffer rinse
at a fixed angle of incidence (related to the amount of the indicates the amount of the material remaining on the
material on the surface) was the same before and after surface. Stability of the final layer is high since there is
purging the 0.5 mL bubble through the cell. Thus no indication of the surfactant or surfactant-polymer
desorption of SDS did not occur. Time measurement complex desorption upon rinsing with water or buffer. On
revealed that introduction of the bubble caused a spike the other hand, as was mentioned above, SDS desorbs
in reflectivity. The magnitude and direction of the spike fast when it is not fixed on the surface by a subsequent
were poorly reproducible. When an air bubble is flushed polymer layer.
through, a thin film of liquid still remains on the substrate. To obtain quantitative information about the SDS-
Calculations show that in a narrow interval of the liquid PDDA complex and find optimum conditions for its
film thicknesses (ca. from 200 to 700 nm), the magnitude formation, we studied the effect of SDS and PDDA
and direction of the reflectivity spike dramatically depend concentrations. Thicknesses of layers and amounts of SDS
on the thickness. Since we cannot control the thickness and PDDA obtained at different concentrations of complex
of the liquid film between the bubble and the solid with components in buffer are compiled in Table 1. The
nanometer precision, the exact appearance of the spikes thickness of the first SDS layer was measured by SPR
was always different. after the equilibrium in SDS adsorption was achieved. It
Kinetics of SDS adsorption from a 1 cmc solution in was followed by PDDA injection, preceded with an air
buffer, subsequent PDDA adsorption from a 0.2 M solution, bubble, and the system was allowed to equilibrate in the
and the following buffer rinse is shown in Figure 2. The cell for a few minutes until the reflectivity reached a
equilibrium reflectivities measured for the SAM, SDS plateau. The thickness of the PDDA layer was obtained
adsorbed on the SAM, and PDDA adsorbed on the SDS after subsequent buffer rinse to a constant reflectivity
are given in Figure 3 as a function of the incident angle. value. One can see from Table 1 that at low SDS
The sequential adsorption of first SDS and then PDDA, concentrations, little PDDA is adsorbed due to the fact
both in phosphate buffer solution, results in a shift in the that the amount of SDS adsorbed in buffer considerably
plasmon resonance peak (or angle) to higher values. This decreases at low SDS concentrations in the bulk (Figure
shift reflects the change in the refractive index and the 1). At the same time, adsorption of PDDA from a more
thickness of the layers adsorbed on the surface. Using the diluted solution (0.05 M) yielded thin layers at any SDS
Fresnel equations, the thickness or surface excess con- coverage. The thickness of the PDDA layer formed at
centration can be calculated (see below). The instanta- optimum conditions ([SDS] g 1 cmc, [PDDA] ) 0.2 M) is
Adsorption onto a Surface-Confined Surfactant Langmuir, Vol. 19, No. 6, 2003 2247

1.1 nm and is in the same range as values obtained for


layer-by-layer polyelectrolyte structures41 and PDDA
layers adsorbed on negatively charged thiol SAMs on
gold.35
To gain further evidence of the formation of the
surfactant-polyelectrolyte complex on the surface that
prevents SDS desorption, we carried out an FTIR study
of the surface complex. Spectra were collected in reflec-
tance mode with the grazing angle of 80. Since both SDS
and PDDA contain CH2 groups having similar adsorption
bands in IR, perdeutero SDS was used in this experiment
to clearly distinguish it from the protonated polymer. It
was also useful by virtue of the experimental procedure
that was employed for surface complex preparation and
isolation for FTIR study. We found that the transfer of a
substrate with the formed surface complex through the
water-air interface resulted in complex desorption,
probably due to the high interfacial tension of pure water.
To reduce the interfacial tension, SDS (perhydro) solution
was spread with a microsyringe on the water surface just
before pulling the slide from the beaker. A SDS monolayer
formed on the water-air interface and lowered the surface
tension to prevent desorption of the SDS-polymer complex
from the SAM. The necessity of using additional reagents
that might contaminate the complex on the surface and
show up in IR spectra was another reason to use
perdeuterated SDS (SDS-d25) for FTIR experiments. FTIR
spectra of SDS-d25 and the SDS-d25-PDDA complex
corresponding to vibrations of the SO3 group are shown
in Figure 4a. We attribute the peak at 1045 cm-1 in SDS-
d25 to symmetric stretching and a broad one at about 1250
cm-1 to asymmetric stretching of the SO3 group.42-44 While
the latter band is too broad to allow precise determination
of its maximum, the former one definitely shifts from 1045
to 1037 cm-1 upon complex formation. It is known that Figure 4. Grazing angle FTIR spectra of SDS-d25 adsorbed on
SO3- modes are sensitive to the nature of the counter- a cysteamine SAM on gold and the SDS-d25-PDDA complex on
cation.44 The IR spectral region corresponding to sym- a cysteamine SAM on gold: (a) 800-1400 cm-1 region, vibrations
metric and asymmetric stretching of CD2 groups45 at 2097 of SO3 group; (b) 2000-2300 cm-1 region, vibrations of CD2
and about 2200 cm-1, respectively, is shown in Figure 4b. group.
The spectra (Figure 4) show that deuterated SDS is still
present on the surface after immersion of the SDS-coated
slide into 0.2 M PDDA solution and subsequent thorough
rinsing with water. If a stable surfactant-polyelectrolyte
complex was not formed on the surface, SDS-d25 would
rapidly desorb from the cysteamine SAM and could not
be seen in IR spectra. Successful formation of the complex
means that the process of SDS desorption is slower than
PDDA interaction with the surface-confined surfactant
and adsorption on the surface. A possible schematic of the
PDDA-SDS complex is shown in Figure 5. When SDS at
or above the cmc is adsorbed on a surface of opposite
charge, it will lead to cylindrical surface micelles aligned
in a common direction.3,8-18,34 Adsorption of PDDA on top
of the surface micelles could lead to the complex shown.
Since PDDA is a random coiling polymer in solution, it is
expected that PDDA will not have significant structure
except for its positive charges interacting close with the
negative charges of the SDS surface micelles. However,
for stiff polymers, like polypeptide helices, Coulombic Figure 5. Schematic drawing of PDDA adsorbed on top of
SDS hemimicelles. The drawing is not to scale.
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B 2000, 104, 11195-11201. molecules on the surface micelles.
(43) Ostrovskii, D.; Kjoniksen, A. L.; Nystrom, B.; Torell, L. M.
Macromolecules 1999, 32, 1534-1540.
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(45) Stroeve, P.; Saperstein, D. D.; Rabolt, J. F. J. Chem. Phys. 1990, In this work, we showed the formation of a surface
92, 6958-6967. surfactant-polyelectrolyte complex on a solid-liquid
2248 Langmuir, Vol. 19, No. 6, 2003 Artyukhin et al.

interface by sequential adsorption of first a surfactant for the surface complex formation were about 1 cmc and
(SDS) and then a polyelectrolyte (PDDA). The complex is 0.2 M, respectively.
stable in aqueous environments and does not desorb or
dissociate upon rinsing with water. Formation of the SDS- Acknowledgment. The MRSEC program of the
PDDA complex was studied by surface plasmon resonance National Science Foundation under Award DMR-9808677
and FTIR. The influence of surfactant and polyelectrolyte supported this work.
concentrations on the formation of the surface complex
was studied. The SDS and PDDA concentrations necessary LA026640S