Obviously, the formation of separated domains
of each component in hydrophilic binary SAMs
significantly depends on the interactions between
like-molecules and unlike-molecules, which are
affected by number of molecules diffused from
solution phase. Therefore, the influence of domain
formation on the solution compositions ( solMeOH)
was studied as shown in Fig.2.
Figure 2: Dependence of charges of: AUT; MUA;
MeOH domains on solMeOH in binary SAMs of
AUT-MeOH (A) and MUA-MeOH (B). Arrows
denote the specific value of solMeOH at which
QAUT = QMeOH and QMUA = QMeOH
As seen in this figure, where the charge (Q) was
estimated from the peak areas on the cyclic
voltammograms recorded for binary SAMs prepared
at various solMeOH. The formation of AUT domains
separated from MeOH domains can be clearly seen
at solMeOH ≈ 0.3 (Fig. 3a), whereas the formation of
MUA domain separated from MeOH domain can be
obtained at solMeOH ≈ 0.6 (Fig. 3b). Furthermore, it is
interesting to see that the value of solMeOH at which
QAUT = QMeOH and QMUA = QMeOH is 0.5 and 0.8,
respectively (denoted by arrows in figures 2a and
2b). The difference in this value of solMeOH suggests
that the formation of MUA domains prevents the
adsorption of MeOH molecules from solution phase
compared with that of AUT. In order to interpret this
phenomenon, Fourier transform infrared
spectroscopy (FTIR) technique was used to study the
structure of single SAMs of AUT and MUA, as
shown in Fig. 3. In this figure, the increase of bands
at 2855 cm-1 and 2965 cm-1, assigned to symmetric
and asymmetric stretching vibrations of CH2,
respectively, of AUT SAM can be clearly seen. This
indicates that the orientation of AUT molecules is
more perpendicular to the Au(111) surface than that
of MUA molecules. Particularly, the kinetic
adsorption of SAMs composed of multi-components
of alkanethiols has been investigated previously
[16], indicating that alkanethiol molecules adsorb on
the surface by initially lying on the flat before
gradually standing up to form tightly packed SAMs.
Thus, in the cases of single SAMs of AUT and
MUA, the standing up of MUA molecules to selfassembly induces less vacant sites on the surface
than that of AUT molecules. This makes a reduction
of possibility for MeOH molecules to adsorb on the
surface in binary SAMs of MUA-MeOH compared
with in binary SAMs of AUT-MeOH. This means
that the value of solMeOH employed for preparation
of binary SAMs of MUA-MeOH should be higher
than that to form binary SAMs of AUT-MeOH, as
obtained results depicted in Fig. 2.
A more evidence reflects the higher degree of
phase separation in binary SAMs of AUT-MeOH
compared with binary SAMs of MUA-MeOH, that
is the peak at E = -0.85 V in the curve recorded for
MUA-MeOH is not sharp like the peak of AUTMUA, its top broads about 100 mV as seen in Fig. 1.
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Vietnam Journal of Chemistry, International Edition, 55(2): 178-182, 2017
DOI: 10.15625/2525-2321.2017-00440
178
Miscibility in two phase-separated binary self-assembled monolayers
composed of hydrophilic components on Au(111)
Pham Hong Phong
Institute of Chemistry, Vietnam Academy of Science and Technology
Received 16 September 2016; Accepted for publication 11 April 2017
Abstract
The typical characteristic of two binary self-assembled monolayer (SAMs) composed of 11-aminoundecanethiol
hydrochloride (AUT), and 10-carboxy-1-decanethiol (MUA) in each and the other was 2-hydroxylethanethiol (MeOH)
was investigated. The dependence of charges (Q), estimated from the peak areas in cyclic voltammograms on the
mixing ratios of components (
sol
MeOH) indicated that QMUA = QMeOH at
sol
MeOH = 0.8, meanwhile QAUT = QMeOH at
sol
MeOH = 0.5, suggesting that adsorbed MUA molecules prevented the adsorption of MeOH molecules. Fourier
transform infrared spectrometry (FTIR) showed the increase of band at 2855 cm
-1
and 2965 cm
-1
, assigned to symmetric
and asymmetric of CH2, respectively, of SAM of AUT, indicating the more perpendicular orientation of AUT molecules
compared with MUA molecules on the Au(111) surface. This result interpreted the degree of phase separation in binary
SAMs of AUT-MeOH compared with binary SAMs of MUA-MeOH.
Keywords. Binary self-assembled monolayers, miscibility, hydrophilic components.
1. INTRODUCTION
Self-assembled monolayers (SAMs) are
nanostructured materials that have been attractive to
many studies because they provide a convenient,
flexible and simple system to tailor the interfacial
properties of metals, metal oxides, and
semiconductors [1]. The most extensively studied
class of SAMs is derived from the adsorption of
alkanethiols on substrates such as gold, silver,
copper, and mercury. The high affinity of thiols for
the surfaces of noble and coinage metals makes it
possible to generate well-defined organic surfaces
with useful and highly alterable chemical
functionalities displayed at exposed interfaces. In
order to tailor the surface properties, two or more
components having different chemical
functionalities have been used to provide more
possibilities in modification. Thus, studies of
characteristics of multi-component SAMs are
essential to understand fundamentals of these types
of nanostructured materials. Such as, studies of
characteristics of various combination of two
alkanethiols by co-adsorption onto Au(111) from a
mixing solution: domain structures of binary SAMs
composed of 3-mercapto-1-propanol and 1-
tetradecanethiol on Au(111) [2], miscibility of 1-
undecanethiol and 11-mercaptoundecanoic acid on
Au(111) [3], phase separation of 2-
mercaptoethanesulfonic acid and 1-octadecanethiol
on Au(111) [4], or ideal nonideality in adsorption of
2-aminoethanethiol and 2-mercaptoethane sulfonic
acid on Au(111) [5]. These results provide basics for
further investigations of many studies on SAMs and
their applications [6-10].
In this context, we recently reported that a binary
SAMs of AUT and MeOH (AUT-MeOH) was
employed as an initial binary SAM for preparing the
phase-separated binary SAMs composed of AUT
and MUA by electrochemically selective
replacement technique [11]. Particularly, co-
adsorption of both AUT and MUA components from
a mixing solution forms a homogenous binary SAMs
[12]. Thus, in order to obtain a phase separation
between these components, it is needed to use
another technique as reported. However, in the
previous work, the combination of two alkanethiols:
AUT and MeOH was employed to prepare the initial
phase-separated binary SAMs, the researchers did
not further focus on investigations to interpret why
this binary SAMs was used instead a binary SAMs
of MUA and MeOH (MUA-MeOH). This is due to
that it requires further systematic investigations, and
thus, is reported in this paper. Here, the
electrochemical behaviors of these binary SAMs
were focused to explain that a combination of AUT
and MeOH has more advantages than that of MUA
and MeOH to employ as an initial binary SAMs.
VJC, 55(2), 2017 Pham Hong Phong
179
Simultaneously, the obtained results were presented
to provide characteristics of these hydrophilic binary
SAMs to support for studies in molecular
engineering in nanostructured materials.
2. EXPERIMENTAL
2.1. Reagents
11-aminoundecanethiol hydrochloride (AUT),
10-carboxy-1-decanethiol (MUA) was purchased
from Donjindo, and 2-hydroxylethanethiol (MeOH)
was purchased from TIC Co. These chemicals were
used without further purification.
Water was purified through a Mili-Q system
(Millipore Co.). All other chemical were of reagent
grade and used without further purification. Au(111)
substrates were prepared by vapor deposition of gold
(99.99 % purity) onto freshly cleaved mica sheets
(Nilaco, Japan) which were baked at 580
o
C prior to
the desorption and maintained at 580
o
C during the
deposition.
2.2. Preparation of the binary SAMs
of AUT-MeOH and MUA-MeOH
Binary SAMs of AUT-MeOH and MUA-MeOH
were prepared by immersing Au(111) substrates for
24 5 h in ethanol solution of these thiols where the
total concentration of thiols was kept at 1 mM. The
composition of these SAMs was controlled by
varying the molar ratio of MeOH,
sol
MeOH, keeping
Ctotal constant. Here,
sol
MeOH was defined by
sol
MeOH
= C
s
MeOH/ C
s
total, and C
s
total = (C
s
MeOH + C
s
AUT) for
binary SAMs of AUT-MeOH, and C
s
total = (C
s
MeOH +
C
s
MUA) for binary SAMs of MUA-MeOH. Binary
SAMs were then rinsed with ethanol and dried in air.
2.3. Apparatus
Cyclic voltammetry for the reductive desorption
of adsorbed thiols was used to examine a surface
composition at each process of the replacement. The
voltammograms were recorded in a deaerated
0.5mol dm
-3
KOH aqueous solution at scan rate of
20 mV/s at 25
o
C. A Au(111) deposited mica coated
with the SAM was mounted at the bottom of a cone-
shape cell using an elastic O-ring. The surface area
of the electrode was estimated to be 0.126 cm
2
. The
potential was referred to an Ag/AgCl (saturated
KCl) electrode.
Fourier transform infrared spectra (FTIR) were
recorded with a Thermo-Matton Infinity
spectrometer equipped with a HgCdTe detector and
a photoelastic modulator (Hinds, PEM-90). The
signal was demodulated with a synchronous
sampling demodulator (GWC Instruments). The
differential reflectance was numerically converted to
absorbance.
3. RESULTS AND DISCUSSION
The characteristics of binary SAMs of AUT-
MeOH and MUA-MeOH were studied by
voltammetry for reductive desorption as presented
representatively in Fig. 1. In order to emphasize the
behaviors, voltammograms recorded for single
SAMs of AUT, MUA and MeOH were also
depicted. It is well known that the peak potential in
voltammograms reflects the Gibbs energy for
reductive desorption of thiolate SAMs [13]. Hence,
among these single SAMs, the desorption of SAM of
MeOH requires the lowest energy due to weak Van
Der Waals interactions between the molecules on
Au(111) surface, giving the appearance of a peak at
-0.60 V. Both SAMs of MUA and AUT possess
stronger Van Der Waals interactions due to having
longer alkyl chains (n), giving more negative peak
potentials, at -0.95 V and -0.97 V, respectively. A
difference of 20 mV between two peaks of SAMs of
AUT and MUA is due to one ethylene unit longer in
SAM of AUT, leading to the requirement of a little
more energy for reductive desorption [14].
Contrarily, voltammograms recorded for binary
SAMs of AUT-MeOH and MUA-MeOH show two
peaks corresponding to the desorption of domains
containing a rich component in each binary SAMs.
As seen in these curves, there is a shift of peaks at
-0.60 V of SAM of MeOH to the negative direction,
meanwhile peaks at -0.95 V and -0.97 V shifts to the
positive direction. These peak shifts clearly indicate
the mutual solubility of components during
adsorption [3, 15].
In order to know reasons for this phenomenon, it
is noted that the adsorption of alkanethiols from
mixing solution on the substrates takes place through
various steps, as briefly described as following: (i)
diffusion from solution phase to the substrate
surface; (ii) binding to atoms on the substrate under
lying down state; (iii) standing up for stabilization
[16]. Hence, in the cases of hydrophilic binary
SAMs of AUT-MeOH and MUA-MeOH, the
formation of domains can be suggested as following:
after diffusion from solution to the Au(111) surface
for adsorption, like-molecules tend to aggregate
together to stabilize domains of AUT or MUA
separated from MeOH domains. This tends to
prevent a mix of unlike-molecules within domains.
Particularly, the peak shifts shown in Fig. 1 reveal
that there is a miscibility of AUT or MUA into
VJC, 55(2), 2017 Miscibility in two phase-separated binary
180
MeOH domains. This is due to adsorbed AUT and
MUA molecules are more surface active than MeOH
molecules because of higher value of methylene
units (n), leading to a surface diffusion into domains
of MeOH. But interestingly, adsorbed MeOH
molecules, having short alkyl chain, can also exist in
AUT or MUA domains, in which Van Der Waals
interactions between AUT or MUA molecules much
stronger than MeOH molecules. This behavior can
be interpreted by repulsive interactions between
deprotonated carboxyl (-COO
-
) and protonated
amino (-NH3
+
) functional groups existing in MUA
and AUT domains, respectively [12], resulting in
vacant sites on the surface for the adsorption of
MeOH molecules. This is a typical characteristic of
this type of hydrophilic binary SAMs. And this is
different from those reported by other authors, in
which binary SAMs composed of a hydrophilic
component having short alkyl chain length and a
hydrophobic one with very long alkyl chain length
forms a clear-cut phase separation between two
components [2, 4, 15].
Figure 1: Cyclic voltammograms for reductive
desorption of single and binary SAMs, recorded in
KOH 0.5 M solution, v = 0.1 V /s
Obviously, the formation of separated domains
of each component in hydrophilic binary SAMs
significantly depends on the interactions between
like-molecules and unlike-molecules, which are
affected by number of molecules diffused from
solution phase. Therefore, the influence of domain
formation on the solution compositions (
sol
MeOH)
was studied as shown in Fig.2.
Figure 2: Dependence of charges of: AUT; MUA;
MeOH domains on
sol
MeOH in binary SAMs of
AUT-MeOH (A) and MUA-MeOH (B). Arrows
denote the specific value of
sol
MeOH at which
QAUT = QMeOH and QMUA = QMeOH
As seen in this figure, where the charge (Q) was
estimated from the peak areas on the cyclic
voltammograms recorded for binary SAMs prepared
at various
sol
MeOH. The formation of AUT domains
separated from MeOH domains can be clearly seen
at
sol
MeOH ≈ 0.3 (Fig. 3a), whereas the formation of
MUA domain separated from MeOH domain can be
obtained at
sol
MeOH ≈ 0.6 (Fig. 3b). Furthermore, it is
interesting to see that the value of
sol
MeOH at which
QAUT = QMeOH and QMUA = QMeOH is 0.5 and 0.8,
respectively (denoted by arrows in figures 2a and
2b). The difference in this value of
sol
MeOH suggests
that the formation of MUA domains prevents the
adsorption of MeOH molecules from solution phase
compared with that of AUT. In order to interpret this
phenomenon, Fourier transform infrared
spectroscopy (FTIR) technique was used to study the
structure of single SAMs of AUT and MUA, as
shown in Fig. 3. In this figure, the increase of bands
-1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0
AUT
MUA
MeOH
2 A
E V
AUT-MeOH (
sol
MeOH
= 0.5)
MUA-MeOH (
sol
MeOH
= 0.8 )
0.0 0.2 0.4 0.6 0.8 1.0
0
20
40
60
80
100
120
Q
/
C
. c
m
-2
AUT
MeOH
sol
MeOH
MUA
MeOH
0
20
40
60
80
100
120
Q
/
C
. c
m
-2
0.0 0.2 0.4 0.6 0.8 1.0
sol
MeOH
VJC, 55(2), 2017 Pham Hong Phong
181
at 2855 cm
-1
and 2965 cm
-1
, assigned to symmetric
and asymmetric stretching vibrations of CH2,
respectively, of AUT SAM can be clearly seen. This
indicates that the orientation of AUT molecules is
more perpendicular to the Au(111) surface than that
of MUA molecules. Particularly, the kinetic
adsorption of SAMs composed of multi-components
of alkanethiols has been investigated previously
[16], indicating that alkanethiol molecules adsorb on
the surface by initially lying on the flat before
gradually standing up to form tightly packed SAMs.
Thus, in the cases of single SAMs of AUT and
MUA, the standing up of MUA molecules to self-
assembly induces less vacant sites on the surface
than that of AUT molecules. This makes a reduction
of possibility for MeOH molecules to adsorb on the
surface in binary SAMs of MUA-MeOH compared
with in binary SAMs of AUT-MeOH. This means
that the value of
sol
MeOH employed for preparation
of binary SAMs of MUA-MeOH should be higher
than that to form binary SAMs of AUT-MeOH, as
obtained results depicted in Fig. 2.
A more evidence reflects the higher degree of
phase separation in binary SAMs of AUT-MeOH
compared with binary SAMs of MUA-MeOH, that
is the peak at E = -0.85 V in the curve recorded for
MUA-MeOH is not sharp like the peak of AUT-
MUA, its top broads about 100 mV as seen in Fig. 1.
Figure 3: FTIR spectra of single SAMs
of AUT and MUA
These clear evidences suggest that the
miscibility of MeOH into AUT domains should be
lower than MeOH into MUA domains. This is a real
advantage of binary SAMs of AUT-MeOH
compared with SAMs of MUA-MeOH in degree of
phase separation. The obtained result, thus, provided
more fundamental knowledge to interpret the
reasons of using binary SAMs of AUT-MeOH as an
initial binary SAMs for selective replacement
technique as we reported in previous works [11].
4. CONCLUSION
In this study, the formation of separated domains
in binary SAMs of AUT-MeOH and MUA-MeOH
was investigated and compared to emphasize the
role of intermolecular interactions in the formation
of domains containing hydrophilic components. The
obtained results are fundamental to interpret the
advantage of binary SAMs of AUT-MeOH used as
an initial SAMs to prepare phase-separated binary
SAMs composed of oppositely charged components
having similar alkyl chains that tends to form
homogenous by adsorption from mixing solution, for
instant, binary SAMs of AUT-MUA as reported.
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Corresponding author: Pham Hong Phong
Institute of Chemistry
Viet Nam Academy of Science and Technology
No. 18, Hoang Quoc Viet, Cau Giay District, Hanoi
E-mail: phphong@ich.vast.vn; Telephone number: (84) 4 38362008.
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