Article

pubs.acs.org/Langmuir

Detection and Characterization of Liquid|Solid and

Liquid|Liquid|Solid Interfacial Gradients of Water Nanodroplets in
Wet NOctyl-2-Pyrrolidone
Christine E. Hay, Frank Marken, and G. J. Blanchard*,

Michigan State University, Department of Chemistry, East Lansing, Michigan 48824, United States
University of Bath, Department of Chemistry, Claverton Down, Bath BA2 7AY, United Kingdom

S Supporting Information
*

ABSTRACT: We report on the rotational diusion dynamics and uorescence lifetime of lissamine rhodamine B sulfonyl
chloride (LRSC) in two thin-lm experimental congurations. These are liquid|solid interfaces, where N-octyl-2-pyrrolidone
(NOP) containing water and ethylene glycol (EG) thin lms are each supported on glass, and a liquid|liquid|solid interface where
thin lms of water and NOP, both supported on glass, are in contact with one another, forming an NOP|water interface. The
reorientation dynamics and uorescence lifetime of LRSC are measured as a function of distance from the NOP|glass and EG|
glass interfaces and from the NOP|water and NOP|glass interfaces in the liquid|liquid|solid experimental conguration.
Fluorescence anisotropy decay data from the liquid|solid systems reveal a liquid lm depth-dependent gradient spanning tens of
micrometers from the NOP|glass interface into the wet NOP phase, while this gradient is absent in EG. We interpret these
ndings in the context of a compositional gradient in the NOP phase. The spatially resolved uorescence lifetime and anisotropy
decay data for an NOP|water|glass interfacial structure exhibits the absence of a gradient in the anisotropy decay prole normal to
the NOP|water interface and the presence of a uorescence lifetime gradient as a function of distance from the NOP|water
interface. The compositional heterogeneity for both interfacial systems is in the form of water nanodroplets in the NOP phase.
We understand this compositional gradient in the context of the relative surface energies of the water, NOP, and glass
components.

INTRODUCTION
The study of liquid|solid interfaces has attracted signicant
interest because of the central role that such interfaces play in
areas ranging from tribology to chemical sensing and
separations to electrode processes and reactions. The
examination of the liquid phase at or near such interfaces
typically relies on the use of techniques that were designed for
the study of bulk liquids, and as such, there is limited
information available on the organization of the interfacial
region. Electrochemical studies have, of course, provided
exquisitely detailed information on the organization of solutions
in contact with electrode surfaces, and there is a wellestablished body of theoretical understanding of the electric
double layer and short-range organization at the electrode
surface itself.13 It is well established that the spatial extent of
surface charge eects is on the order of hundreds of
nanometers to a few micrometers at most.410 Beyond this
distance it is held that the liquid phase behaves in the same
manner as the corresponding bulk liquid.
2014 American Chemical Society

Many processes of central importance to chemical and

physical events that occur at the liquidsolid interface can
extend over micrometer length scales. Diusion, precipitate
formation, and the existence of temperature gradients are three
examples. It is thus of fundamental interest to understand the
limit(s) to the validity of the assumption that liquids located at
the liquidsolid interface behave as bulk liquids over distances
on the order of micrometers. In the rst of two experimental
congurations, we report on two chemical systems: one that is
expected to behave as a bulk liquid and one that has the
potential to exhibit anomalous behavior. The two systems
studied are ethylene glycol (EG) and wet N-octyl-2-pyrrolidone
(NOP), each at a borosilicate glass interface. EG is miscible
with water in all proportions and is expected to exhibit
properties of a bulk liquid in the presence or absence of water,
Received: July 11, 2014
Revised: August 6, 2014
Published: August 7, 2014
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whereas amphiphilic NOP is not completely miscible with

water. NOP readily phase separates from water at room
temperature and has a lower consolute temperature below 0
C.11,12 The solubility of water in NOP is not reported
explicitly, although phase diagrams indicate a single phase may
exist at water concentrations of less than 40% (w/w).12,13 The
low miscibility of water in NOP as well as the possibility of the
formation of secondary structures in the presence of water
provides an opportunity for anomalous behavior.
While there are a variety of ways to study the liquid|solid
interface, examining such an interface with a depth resolution of
less than 1 m and an operating depth range on the order of
100 m and providing spatially localized information on
viscoelastic properties can be a signicant challenge. We use a
confocal scanning microscope equipped with time-resolved
detection gear to resolve the uorescence lifetime and
reorientation dynamics of a chromophore in the liquid phase
with ca. 50 ps time resolution. The lateral resolution of this
system is on the order of the diraction limit (ca. 250 nm), and
the depth of focus is less than 1 m for a 100 objective. Using
this instrument, we previously demonstrated the ability to
obtain uorescence lifetime and anisotropy decay images for
planar supported lipid bilayer structures.14,15 This is the rst
report utilizing this instrument primarily for its ability to
achieve depth resolution as opposed to lateral resolution. We
have found that the lifetime and anisotropy decay dynamics of a
rhodamine chromophore behave in the expected manner as a
function of distance from the solvent|glass interface for the EG
solvent. For the interface between wet NOP and glass, we
resolve a depth-dependent gradient in uorescence anisotropy
decay dynamics that persists for tens of micrometers into the
liquid phase. Using the information from these two interfacial
systems, we are able to identify the presence of a compositional
inhomogeneity in the wet NOP system, and we consider the
possible origins of this interfacial gradient.
In the second experimental conguration, we characterize a
thin lm NOP|water interface supported on glass to assess the
behavior in the presence of a liquid|liquid interface. We
measure the rotational diusion behavior of this chromophore
as a function of the (micrometer-scale) distance from the
interface and as a function of the distance from the glass
support. The data reveal a gradient in the anisotropy decay time
constants normal to the NOP|glass interface consistent with the
results of the rst experimental conguration and an absence of
the water nanodroplet size gradient normal to the NOP|water
interface. We do nd evidence for a gradient in the
concentration of water nanodroplets normal to the NOP|
water interface, and these ndings are consistent with the
nanoemulsion size being mediated by the surface energies of
the NOP|water and NOP|glass interfaces. Taken collectively,
the data reported on these liquid|liquid and liquid|solid
interfaces can be understood in the context of the existence
of water nanodroplets in the wet NOP phase with the size and
concentration of the nanodroplets depending on the interface
between NOP and the liquid or solid phase with which it is in
contact.

Figure 1. (Top) Structure of lissamine rhodamine B sulfonyl chloride

(LRSC). (Bottom) Structure of N-octyl-2-pyrrolidone (NOP).

system (Millipore). For steady-state absorbance and emission

measurements, the chromophore concentration was 104 M in water
and dry NOP. The concentration of LRSC in EG was 105 M. Upon
exposure to water, the chromophore is likely hydrolyzed to the
sulfonic acid. We refer to the chromophore as LRSC throughout
because we have not veried the hydrolysis reaction for each system.
The sample holder for optical measurements on the microscope was
an Attouor cell chamber (Invitrogen) tted with a round borosilicate
glass coverslip (25 mm diameter, no. 1.5, Thomas Scientic). In order
to contain the liquid samples in a smaller area, a glass microscope slide
(1 mm thick, 1.7 cm diameter, Globe Scientic) with a bored hole
(inner diameter of 5.1 mm) was placed in the sample holder. Solutions
of 104 M LRSC in dry NOP were exposed to water for 3 h, and then
approximately 150 L was deposited in the center of the bored
microscope slide onto a clean glass surface. Excess liquid lled the
space between the glass surface and the microscope slide. NOP|water|
glass interfaces were formed by adding approximately 150 L of MilliQ water to the cell chamber and then depositing 0.01 L of 104 M
LRSC in dry NOP in the well in the center of the microscope slide. A
side-by-side interface with a thickness of 500 m formed on the glass
coverslip surface. The coverslips were cleaned prior to use by
immersion in piranha solution (a 3:1 ratio of concentrated sulfuric acid
and 30% hydrogen peroxide) for 30 min. (Caution! Piranha solution is
a strong oxidizer.) An alternative method of cleaning the borosilicate
glass slides was rinsing with ethanol prior to exposure to UV-generated
ozone for 15 min.
Steady-State Measurements. Steady-state absorbance measurements were made with an ATI Unicam double-beam UVvisible
absorbance spectrophotometer over the range of 400 to 700 nm at a
spectral resolution of 1 nm for all measurements. Steady-state
spontaneous emission spectra were recorded using a Jobin-Yvon
Fluorolog III spectrometer over the range of 550 to 700 nm. The
excitation wavelength was set to 540 nm for LRSC in water and NOP
emission spectral acquisition.
Time-Correlated Single-Photon Counting (TCSPC). The
uorescence lifetime and anisotropy decays were collected with the
time-resolved uorescence imaging instrument described previously.15
A brief description of the instrumental setup is provided here. The
light source for the system is a CW mode-locked Nd:YVO4 laser that
produces 13 ps pulses at 1064 nm with an 80 MHz repetition rate
(Spectra Physics Vanguard). The Nd:YVO4 laser second or third
harmonic output excites a cavity-dumped dye laser (Coherent 702-2),
with output characterized by 5 ps pulses at wavelengths of between
430 and 850 nm. The repetition rate of the laser is adjustable between
80 kHz and 80 MHz using the cavity-dumping electronics. The dye
used to excite the samples is pyrromethene 567 (Exciton), providing

EXPERIMENTAL SECTION

Materials. Chromophore lissamine rhodamine B sulfonyl chloride

(LRSC) (Figure 1, 99% Acros Organic) was used as received. NOctyl-2-pyrrolidone (NOP, Figure 1, 98% Aldrich) and ethylene glycol
(EG, 99%, Macron Fine Chemicals) were used as received. Water
used in these studies was puried in-house with a Milli-Q ltration
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Figure 2. Schematic of sample and optical excitation/collection congurations for (a) NOP|glass and EG|glass interfaces (NOP|glass interface
shown) and for (b) an NOP|water|glass interface.
excitation wavelengths of between 560 and 600 nm. The average
power at the sample is 1 mW or less.
A vertically polarized pulse of light is input into an inverted optical
microscope (Nikon Eclipse Ti-U) through a confocal scanner (Becker
& Hickl DCS-120). The excitation pulses pass through the microscope
objective, and the focused beam can be localized at one position or
rastered across the surface of the sample using the galvo-drive unit
(Becker & Hickl GDA-120) in the confocal scanner. The emission
collected by the microscope objective is split into parallel and
perpendicularly polarized signal components in the confocal scanner,
passed through long-pass and bandpass wavelength-selection lters,
and detected using two avalanche photodiode detectors (IDQuantique ID100). TCSPC detection electronics (Becker & Hickl
SPC-152) are used for signal processing and collection. SPCM
software (Becker & Hickl) for a Windows-based PC is used to control
the data-acquisition parameters.
An oil-immersion microscope objective (Nikon, 100 magnication, NA 1.45, working distance 0.13 mm, depth of eld ca. 0.45 m)

was used for all data acquisition, and the experimental setups are
schematized in Figure 2. Depth proles were generated by collecting
individual data sets in triplicate with the beam parked at a xed
position. The positions along the x axis were xed using the SPCM
galvanometer control window, and the depth along the z axis was
controlled mechanically. The time-resolved uorescence data were
analyzed using MicroCal Origin Pro v. 9.0 to obtain uorescence
lifetime and anisotropy decay time constants.
Dynamic Light Scattering (DLS). Particle size determinations
were made by dynamic light scattering using a Malvern Zetasizer Nano
ZS with a 632.8 nm light source for dry NOP and NOP exposed to
water. All measurements were made at 20 1 C. The wet NOP was
prepared by adding dry NOP to a layer of water in a glass vial, where
NOP was 6.67% (v/v). The NOP layer was removed and analyzed by
DLS.
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RESULTS AND DISCUSSION

An important area of understanding in interfacial science is the

role that one phase plays in mediating the organization of the
other phase(s) in contact with it. This is a well-explored and
well-understood area in the context of solution|electrode
interfaces, for example, where control over the potential of
the electrode surface allows for the evaluation of short-range
electrostatic or Coulombic forces with respect to solution-phase
local organization. It is understood that the spatial extent of the
electric double layer is less than 1 m, typically much less.1,2,16
We examine here a gradient in the uorescence anisotropy
decay dynamics of LRSC in NOP present at a glass surface as a
function of the distance from the surface. This gradient is
anomalous because of its spatial extent, and we are concerned
with understanding the fundamental reason(s) for its existence.
Achieving this understanding will allow for such gradients to be
predicted and, possibly, the extent and nature of the gradient to
be controlled for predetermined purposes.
The instrumentation we have used to acquire information on
interfacial organization and dynamics is designed to image in
the plane of the sample (x, y).14,15 For the work we report here,
we examine two experimental congurations: in the rst
system, the sample is uniform in the x, y plane (Figure 2a), and
the second system is characterized by a single NOP|water
interface in the y, z plane (Figure 2b). For the NOP|glass and
EG|glass interfaces, we have examined the depth (z) dependence of the chromophore lifetime and dynamics, and for the
NOP|water|glass interface, we have examined the x and z
dependencies of the chromophore lifetime and dynamics in the
NOP phase (LRSC preferentially partitions into the NOP
phase, see Figure S-4). Because this imaging instrument is
confocal, the z resolution (depth of focus) is submicrometer,
and the data have been acquired at 10 m z intervals. Each data
point presented is the average of at least ve individual
measurements, with the uncertainties being reported as the
standard deviation (1) of the average of the individual
acquisitions.
The results from the NOP|glass and EG|glass thin lms are
presented rst. The uorescence lifetimes and anisotropy
decays plotted as a function of distance (z) from the NOP|glass
interface (Figure 3) contain several important features. The rst
is that at the interface the chromophore is adsorbed on or
interacting with the glass support and its uorescence lifetime
and anisotropy decay time constants are dierent than for the
liquid NOP layer. This is not surprising given the polar nature
of the chromophore and the piranha-cleaned glass surface and
the comparatively less-polar NOP solvent. The second feature
of note is that, to within the experimental uncertainty, the
uorescence lifetime is constant as a function of depth in the
wet NOP layer. This is also not a surprising result. The third
feature contained in these data is the depth dependence of the
anisotropy decay time constant. The existence of a depth
dependence is reproducible and unexpected. The aim of this
work is to describe the physical and chemical basis for this
nding.
Given the inherently charged nature of the glass interface, it
is important to consider any potential role of Coulombic/
electrostatic forces in producing the results shown in Figure 3.
The spatial extent of Coulombic eects is related to the
propensity of the medium to screen charge, and for polar
systems containing electrolytes, the spatial extent of the
Coulombic eects that give rise to the electric double layer

Figure 3. Dependence of LRSC on the wet NOP uorescence lifetime

() and anisotropy decay time constant () on distance from the
NOP|glass interface. The line drawn through the uorescence lifetime
data is intended as a guide to the eye. The glass support was cleaned
with piranha solution and rinsed with water prior to use. Refer to
Figure 2a for the experimental conguration and the x, y, z coordinate
designation. R(t) data are provided as Supporting Information.

and the diuse double-layer regions is typically under 100 nm.

For nonpolar systems that contain very few charged species, the
spatial extent of surface charge eects can be longer, but in any
event such eects operate on the submicrometer length scale,
and the eect we observe persists for tens of micrometers. In
principle, it is also possible that the surface preparation
methodology could result in contamination that could account
for the gradient. We have evaluated this possibility
experimentally (Supporting Information) and have found that
the same anisotropy decay gradient is seen with two dierent
methods used for cleaning the glass surface.
For these reasons and the extent of the gradient in the
anisotropy decay times in the NOP|glass system that we
observe experimentally (Figure 3), we assert that neither
Coulombic nor contaminant-related eects play signicant
roles in the phenomenon we observe. We believe that the
explanation for the anisotropy decay gradient is related to a
compositional gradient in the liquid (NOP) phase. We have
exposed NOP to deionized water with the expectation that the
solution will reach an equilibrium water concentration in NOP
after a few hours. Because the solvent system we use is a binary
system, there is the opportunity for a compositional gradient to
exist. There is potential for the composition of the liquid near
the NOP|glass interface to be aected by the adsorption of
NOP as has been observed for other nonionic1719 and
ionic2022 surfactants. As a result of adsorption, micelles,
hemimicelles, monolayer, or bilayer structures may form at the
solid surface depending on the concentration and interaction
with surface charge.23 However, the spatial extent of the
secondary structures would only be on the order of nanometers
and would not account for the micrometer-scale gradient we
observe. Additionally, NOP and longer-chain N-alkyl-2pyrrolidones are known to form micelles only in the presence
of cosurfactants.11,24,25 We return to the discussion of the
observed compositional gradient after evaluating the generality
of the phenomenon.
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phenomena. The chemical information of interest is contained

in the functional form and time constant(s) of the decay of
R(t). In this work the chromophore is not tethered to either a
solvent molecule or to the glass interface, and its motion can be
considered in the context of a free rotor, i.e., R() = 0, a
condition that is enforced by tail-matching the polarized
emission transients. Chuang and Eisenthal26 have developed
the theoretical framework for relating the Cartesian components of the rotational diusion constant, D, and the angle
between the excited and emitting transition dipole moments to
the time constants and prefactors of the exponential decay(s)
contained in the experimental R(t) data. Chromophore LRSC
is characterized by a nominally planar system, and the S1
S0 transition is polarized along the chromophore ring system
long axis (x).27,28 For these conditions, a single-exponential
decay of R(t) is consistent with reorientation as a prolate rotor,
and a two-component exponential decay is consistent with
reorientation as an oblate rotor. For all of the measurements we
report here, R(t) decays as a single exponential, and the
anisotropy decay time constant is given by OR = (6Dz)1. Even
with the limited information provided by a single exponential
decay component, where only one Cartesian component of the
rotational diusion constant is sensed, we can speak to the
possible reasons for the gradient we observe.
The anisotropy decay time constant is related to the size of
the reorienting moiety, the viscosity of the surrounding
medium, and the temperature of the system through the
modied DebyeStokesEinstein (DSE) model,29

If the anisotropy decay gradient that we observe is indeed

related to a compositional gradient in the wet NOP phase, then
the replacement of NOP with a dierent solvent system,
particularly one which is miscible with water in all proportions,
should alter the gradient. We show in Figure 4 the uorescence

Figure 4. Dependence of LRSC in the EG uorescence lifetime ()

and anisotropy decay time constant () on distance from the EG|glass
interface. The lines drawn through the uorescence lifetime data ()
and the anisotropy decay data (---) are intended as guides to the eye.
The glass support was cleaned using piranha solution and rinsed with
water prior to use. Refer to Figure 2a for the experimental
conguration and the x, y, z coordinate designation. R(t) data are
provided as Supporting Information.

OR =

R (t ) =

(1)

I (t ) I(t )
Ifl(t )

(3)

where is the viscosity of the bulk solvent, V is the

hydrodynamic volume of the reorienting entity, f is a term
describing the frictional interaction between the reorienting
moiety and the surrounding medium (0 < f 1), kBT is the
thermal energy term, and S is a shape factor to account for the
nonspherical shape of the chromophore.30 We calculate the
hydrodynamic volume of LRSC to be 560 3 using the method
of van der Waals increments,31 and the shape factor S has been
determined for rhodamine chromophores to be S = 0.9.27 Using
this information and the bulk solvent viscosity of = 5.6 cP for
NOP,32,33 we obtain an estimate of OR = 862 ps from eq 3.
This estimate is signicantly lower than the anisotropy decay
time constants we have observed experimentally for the NOP|
glass interface. The data in Figure 3 show OR varying from ca.
2100 ps near the glass surface to ca. 1800 ps 100 m from the
interface.
It is fair, of course, to question the accuracy or validity of the
DSE model for this application. We can gauge the accuracy of
the DSE model by comparing its predictions to experimental
data for a system that is not seen to behave in an anomalous
manner. For LRSC in EG we observe OR for distances of 10
100 m from the interface of 2320 38 ps. Taking the
viscosity of EG to be 16.1 cP at 25 C,34 with f = 1 (stick limit)
and S = 0.9,27,28 we calculate OR = 2435 ps. The slight
dierence between experiment and theory is compelling
evidence for the accuracy and applicability of the modied
DSE model for these data. While the LRSC/EG interactions
and the LRSC/NOP interactions may dier, it is the zdependent trend in the data that is of primary importance here,
and we consider how that trend can be explained in the context
of eq 3.

lifetime and anisotropy decay data for LRSC in EG as a

function of distance from the EG|glass interface. The
uorescence lifetime data for LRSC in EG resemble those for
LRSC in wet NOP, exhibiting depth-independent lifetimes for
the chromophore away from the surface and a dierent lifetime
for the chromophore interacting with the glass interface (depth
= 0). The anisotropy decay data for LRSC in EG exhibit a
depth independence to within the experimental uncertainty, in
sharp contrast to the data for wet NOP. The behavior of LRSC
at the EG|glass interface is an expected result, and this nding
points to the NOP system exhibiting a compositional gradient.
We turn next to the possible reasons for the observed
compositional gradient.
We cast the following discussion of these anisotropy decay
data and the physical/chemical basis for them in the context of
known models of rotational diusion. The uorescence lifetime
and anisotropy decay data are derived from polarized
uorescence transients. The sample is excited with a polarized
picosecond pulse of light, and the emission from the sample is
collected for polarizations parallel (I(t)) and perpendicular
(I(t)) to that of the excitation pulse. The uorescence lifetime
and anisotropy decay functions are formulated according to eqs
1 and 2,

Ifl(t ) = I (t ) + 2I(t )

Vf
1
=
6D
kBTS

(2)

For all cases, we observe a single-exponential decay of Ifl(t),

indicating the absence of anomalous excited-state relaxation
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scattering (DLS) data (vide infra). We show in Figure 5a the

calculated number of water molecules surrounding the LRSC

In considering the discrepancy between the simple estimate

from the DSE model (eq 3) and the experimental results, there
are a limited number of ways to account for the data shown in
Figure 3. Specically, the temperature remains constant, we
presume the chromophore does not change shape as a function
of proximity to the glass surface, and the viscosity of NOP does
not vary with proximity to the surface. Within the framework of
the DSE model, the most physically reasonable means of
accounting for the anisotropy decay gradient is through a
gradient in the hydrodynamic volume of the reorienting entity.
We recognize that the gradient in OR corresponds to changes
in Vf and that these terms cannot be separated cleanly.
Despite this limitation, we assert on physical grounds that the
most plausible change is occurring with the eective hydrodynamic volume of the reorienting species. Deviations from the
modied DSE equation have been reported previously in binary
systems, where specic solutesolvent interactions and
consequent changes in the hydrodynamic volume have been
cited as reasons for nonconformity to model behavior.3538
Stevenson et al. reported a compositional dependence in the
reorientation times of 4-benzylamino-7-nitrobenzylfurazan
(BBD) in 1-propanol/water binary systems, where the
hydrodynamic volume of the reorienting entity was found to
change on the basis of the inclusion of interacting solvent
molecule(s).38
In the case of the wet NOP system, the change in
hydrodynamic volume of the reorienting entity can be
accounted for in the context of the chromophore residing in
a primarily aqueous environment that is surrounded by NOP
molecules, and the reorienting entity is (LRSCnH2O), with n
being the depth-dependent quantity. In this model, the
reorienting entity would be a nominally spherical chromophorewater complex (S = 1). To account for the reorientation
times observed experimentally, we add nH2O molecules (21 3
each), as shown in Table 1. The results of this model show that
there is a monotonic trend in the number of water molecules
surrounding the chromophore, decreasing with increasing
distance from the interface. The number of water molecules
in this model ranges from ca. 36 to ca. 48, a number that we
believe to be consistent with absorbance and dynamic light

Figure 5. (a) Calculated number of water molecules in the immediate

proximity of LRSC as a function of distance from the NOP|glass
interface. (b) Calculated diameters of the reorienting entities
containing the chromophore and the number of water molecules
indicated in (a) as a function of distance from the NOP|glass interface.

chromophore, n, as a function of distance from the interface,

and in Figure 5b, we show the calculated diameter of the
chromophorewater entity as a function of distance from the
interface.
An important consideration is why the chromophore within
the water droplet does not simply reorient as though it resided
in bulk water with the NOP|water interface being decoupled
from the LRSC/water interactions. To evaluate this issue, is it
instructive to consider the relative sizes of the water
nanodroplets and the bare chromophore. As noted above, the
calculated hydrodynamic volume for LRSC is 560 3, and if this
volume is taken to be spherical, then it corresponds to a
diameter of 1.02 nm. The water nanodroplets are measured by
DLS to have a diameter of 1.26 0.25 nm (vide infra),
indicating a dierence in diameter of 0.24 nm. The
implication of this comparison is that the sizes of the bare
chromophore and the water nanodroplets are suciently close
that the decoupling of the chromophore/water and water/NOP
interactions is not possible. In other words, the relative sizes of
the chromophore and water nanodroplets are similar enough
that the chromophore/water moiety needs to be treated as a
single reorienting species.
There are two testable predictions of this model. The rst is
that the chromophore nds itself in a local environment
inuenced strongly by the presence of water. The absorption
spectrum of LRSC is sensitive to the presence of water. We
show in Figure 6 the absorption spectra of LRSC in water, dry
NOP, NOP saturated in water, and LRSC in NOP after
extraction from water. The latter two spectra are overlapped. As
can be seen from these data, the LRSC chromophore nds itself
in a primarily aqueous environment in the water-saturated
NOP solution, consistent with the explanation put forth for the
anisotropy decay gradient.

Table 1. Estimated Number of Water Molecules

Surrounding LRSCa
OR calc (ps)

Vtotal (3)

Vwater (3)

d (nm)

1824
1853
1882
1911
1941
1970
1999
2028
2057
2086
2115
2144
2173

1316
1337
1358
1379
1400
1421
1442
1463
1484
1505
1526
1547
1568

756
777
798
819
840
861
882
903
924
945
966
987
1008

36
37
38
39
40
41
42
43
44
45
46
47
48

1.36
1.37
1.37
1.38
1.39
1.39
1.40
1.41
1.42
1.42
1.43
1.43
1.44

a
The number of water molecules, n, between 36 and 48 is used to
determine the hydrodynamic volumes of water (Vwater) and a total
volume (VLRSC + nVwater), which is used to calculate model
reorientation times, OR calc. Diameters, d, are calculated by assuming
a spherical hydrodynamic volume.

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a value that is expected to be smaller than what we observe at

and near the glass interface based on the existence of the
anisotropy decay gradient.
The experimental anisotropy decay data for LRSC in wet
NOP are consistent with a gradient in the average size of the
chromophorewater cluster increasing with proximity to the
glass interface, and this nding is not expected for a simple
solution-phase system, such as EG. It is important to consider
the implications of this nding. The rst implication is that
NOP and water, at least up to saturation concentration, exist as
a colloidal system. When viewed in this context, it is reasonable
to expect there to be a distribution of colloidal nanodroplets
(i.e., water and water + chromophore) suspended in NOP. In
fact, there is precedent for the existence of such nanoscale
heterogeneity being induced in liquid-crystalline systems by the
presence of a small amount of water.39 One possible
explanation for the existence of a gradient in the size of the
colloidal suspension of water nanodroplets is that there is a
dierence in the surface energy for the NOP|glass and NOP|
water interfaces, and the size gradient in the water nanodroplets
represents a gradient in the Laplace pressure of the nanodroplets to compensate for the dierence in surface energies of
the two interfaces. At the point where the NOP, water
nanodroplet, and glass are in contact, there is a single Laplace
pressure that characterizes the resulting structure, and that
Laplace pressure is dierent than for the water nanodroplet in
the NOP phase. Diusion-mediated transport of water
nanodroplets occurs and water molecules are shed from the
nanodroplet to achieve the equilibrium Laplace pressure. This
explanation requires that the shedding of water molecules
occurs on a time scale similar to that of nanodroplet diusion,
giving rise to a gradient in nanodroplet size over the length
scale we observe. A prediction of this explanation is that
dierent interfaces with wet NOP would give rise to dierent
nanodroplet gradients, and, in particular, the NOP|water planar
interface should not exhibit a water nanodroplet size gradient.
We consider this system next. It is important to keep in mind
that the range of the compositional gradient is on the order of
10 water molecules in a cluster, and the use of rotational
diusion allows the resolution of this subtle compositional
gradient.
Another issue is that for the two-phase NOP|glass system
there is a limited amount of water present, and for
thermodynamic reasons, the water concentration should be
uniform throughout the solution. For this reason, the dielectric
constant of the system should be nominally constant, consistent
with a depth-independent uorescence lifetime of the
chromophore. The situation is expected to be dierent when
excess water is available to the NOP phase.
The issue of hindered Brownian diusion of nanoscale
droplets near a solid surface may play a role in these data as
well. Near a solid surface, Brownian diusion in the liquid
phase becomes anisotropic, with motion parallel to the surface
remaining more similar to that in the bulk than motion normal
to the surface.4043 Interfacially-mediated hindered Brownian
diusion of a nanoparticle near a solid surface can be
understood in terms of the surrounding liquid being the source
of momentum due to uctuations in density. As the solid
surface is approached, such uctuations diminish to the level of
phonons in the solid, leading to slower diusion near the
surface. While the length scale of this eect (micrometers) is
too short to account for the anisotropy decay gradient we
observe (Figure 3), it can play a role in mediating the rate at

Figure 6. Absorption spectra of LRSC in water (), LRSC in dry

NOP (---), LRSC in NOP after extraction from water (...), and LRSC
in NOP after equilibration with water (--).

The second prediction of the model is that if these data are

the result of a water nanoemulsion then there should be
detectable droplets present in the solution. We have used DLS
to evaluate whether this is the case. We show these results in
Figure 7, indicating the presence of species with a diameter of

Figure 7. DLS data showing the size distribution of water

nanodroplets present in wet NOP after exposure to water () and
dry NOP (), showing their absence in the same size range as the
water nanodroplets. For all DLS measurements, no chromophore was
present.

1.26 0.25 nm in the water-containing (wet) NOP solution.

An absence of DLS signal is seen in this same size region for
dry NOP (Figure 7). For all DLS measurements, no
chromophore was present. Comparing these results to those
shown in Table 1 and Figure 5b, we assert that this represents
excellent agreement between experiment and the model. While
the results of the model calculation are in agreement with the
experimental data to within the experimental uncertainty, the
values predicted by the model appear to be consistently higher
than those determined by DLS. The DLS measurement
samples the bulk solvent system whereas the reorientation
data are for the solution near the interface, where the
anisotropy decay gradient is observed. Even at a depth of 100
m, which is our experimental limit with the time-resolved
measurement, the trend in size for the chromophorewater
entity appears to be decreasing. Thus, a bulk (DLS)
measurement of the size of the water domains would provide
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It is instructive to examine the spatial dependence of the

uorescence lifetime for this system. In contrast to the
rotational diusion data, position-dependent (x) uorescence
lifetime data are seen in the NOP phase with the addition of the
NOP|water interface normal to the NOP|glass interface as a
function of distance from both interfaces (Figure 9). There is a

which nanodroplets diuse from the surface. Also, to the extent

to which translational and rotational diusional motion are
coupled,44 such interfacial eects could be responsible for the
functional form of the anisotropy decay gradient data we see in
Figure 3 near the wet NOP|glass interface. It is useful to note
that this eect is not expected to play a role in the liquidliquid
interface which we consider next.
In the next section, we examine the NOP|water|glass system
depicted in Figure 2b. On the basis of our ndings from the
NOP|glass system, it is necessary to examine the spatial
dependence of the reorientation time seen in the NOP|water|
glass system. For the three-phase system, we observed no (x, y)
positional dependence of the reorientation time save for
surfacechromophore interactions (Figure 8), while a (z)

Figure 9. (a) Fluorescence lifetime as a function of distance from the

NOP|glass interface for three dierent distances from the water
interface. (b) Fluorescence lifetime as a function of distance from the
NOP|water interface for six dierent distances from the NOP|glass
interface. Experimental error bars representing the standard deviation
are shown for each data point. Refer to Figure 2b for the experimental
conguration and the x, y, z coordinate designation.

steep decline in uorescence lifetime moving away from the

glass support (z axis) while the changes in lifetime as a function
of distance away from the NOP|water interface (x) are modest.
The uorescence lifetime of LRSC is sensitive to spatial
variations in the polarity of its environment, and spatially
resolved lifetime data can be used to infer variations in the
dielectric constant () of the system.4749 The presence of
water nanodroplets in NOP provides for droplet-concentrationdependent variations in the dielectric constant of the liquid
medium. There is a phenomenological relationship between the
rhodamine uorescence lifetime and dielectric constant,50 and
we use this relationship to estimate the spatial dependence of
the dielectric constant (Figure 10). The observation of a spatial
dependence of for this system, with two distinct interfaces,
and the absence of a corresponding spatial dependence in
uorescence lifetime for the case where there is only the NOP|
glass interface indicate a compositional gradient in the NOP|
water|glass system. We assert that the compositional gradient
we observe normal to the NOP|water interface is not a gradient
in the size of the water nanodroplets in NOP but rather a
gradient in the concentration of water nanodroplets in the
NOP.
The lifetime gradient data seen for the three-phase NOP|
water|glass system stand in contrast to the absence of a lifetime
gradient in the two-phase (NOP|glass) system. We did not
observe a dielectric constant gradient in the wet NOP liquid
phase because there was a xed concentration of water in the
system, determined by the exposure of NOP to water initially

Figure 8. (a) Reorientation time and (b) calculated number of water

molecules as a function of distance from the NOP|water interface.
Refer to Figure 2b for the experimental conguration and the x, y, z
coordinate designation.

depth dependence does exist for distances of ca. 40 m and

greater from the NOP|water interface (data not shown) and is
consistent with the previously described NOP|glass system. The
number of water molecules in closest proximity to LRSC and
contributing to the hydrodynamic volume of the reorienting
entity is found to vary in number from 2030. Given the
presence of water in the NOP, it is presumed that the water
domains are at least the same size as those seen for the NOP|
glass system described above; however, we observe smaller
water domains. For this reason, it may appear anomalous that
the anisotropy decay time constants for the NOP|water|glass
system are faster than they are for the system with only the
NOP|glass interface. This is, however, an expected result for an
emulsion. There is a substantial body of literature on the
subject of emulsions, and it is known from this literature that
the viscosity of the uid depends inversely on the average size
of the emulsion inclusion domains.45,46 We would expect this
eect to become signicant only under conditions where there
is a relatively high density of water nanodroplets. Thus, the
faster reorientation times seen for the system characterized by
both water and glass interfaces imply that the average size of
the water domains for this system is larger than for the system
with only the glass interface.
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average size. This is an expected result based on surface energy

considerations, where the NOP|water interface is characterized
by a surface energy essentially the same as that of the water
nanodroplets in bulk NOP. Normal to the NOP|glass interface
and parallel to the NOP|water interface there is a gradient in
the size of the water nanodroplets, manifested in the anisotropy
decay gradient, which can also be understood in terms of
interfacial surface energies.

CONCLUSIONS
We have reported on two distinct thin-lm-supported
interfaces. The rst type is a two-component interface, with
thin layers of liquid NOP or EG supported on glass. We
observe a gradient in the anisotropy decay time for the LRSC
chromophore in wet NOP. The anisotropy decay times
observed vary in a regular manner with the distance from a
glass interface (z), and this gradient is not seen for LRSC in EG
in the proximity of a glass interface. We understand these data
in the context of a compositional gradient in the wet NOP
solvent system, where the species we detect is LRSC in water
nanodroplets within the NOP phase. The chromophorecontaining water droplets are found to vary in size (hydrodynamic volume) as a function of distance from the glass
surface. Anisotropy decay data in conjunction with the modied
DSE model point to a progression in the number of water
molecules associated with a chromophore molecule with
increasing proximity to the glass surface. The size of the
water nanodroplets is estimated from these data to be on the
order of 1.31.4 nm in diameter, and dynamic light scattering
of the colloidal suspension reveals the presence of nanodroplets
that are ca. 1.26 nm in diameter, on average. We view this as
excellent agreement because the DLS measurements sample all
nanodroplets in the suspension, whereas the anisotropy decay
data sample only those droplets in close proximity to the glass
surface. The existence of the gradient is consistent with a
dierence in the surface energies of the wet NOP|water
nanodroplet interface and the NOP|glass interface. No
analogous organization is found in a solvent system (EG)
that does not exhibit phase-segregation issues.
We have also investigated a system composed of two
interfacesan NOP|water interface and an NOP|glass interfacenominally perpendicular to one another. Characterizing
this two-interface system by means of spatial variations in the
uorescence lifetime and anisotropy decay constant has shown
that there are dierent compositional gradients, with one
perpendicular to the NOP|glass interface and one perpendicular
to the NOP|water interface. Normal to the NOP|water interface
is a gradient in the concentration of water nanodroplets of
constant average size, and normal to the NOP|glass interface is
a gradient in the average size of the water nanodroplets. We
understand the reason for dierent types of water nanodroplet
gradients in the context of dierences in the surface tension for
the NOP|glass and NOP|water interfaces. A clear implication of
these ndings is that nanoemulsion size gradients can be
controlled through the identity of the solid support with which
the nanoemulsion is in contact.

Figure 10. (a) Dielectric constant as a function of distance from the

NOP|glass interface for three dierent distances from the water
interface. (b) Dielectric constant as a function of distance from the
NOP|water interface for six dierent distances from the NOP|glass
interface. Refer to Figure 2b for the experimental conguration and the
x, y, z coordinate designation.

and by the amount of adsorbed water at the glass surface. While

there is variation in the diameter of the water nanodroplets
resulting in a size gradient, for any given region of the sample
the total amount of water present remains nominally the same.
For this reason, there is no expectation of a dielectric gradient
in this system. For the three-phase system, where (excess)
water is in contact with both the NOP and glass phases, it is
possible for there to be not only a size gradient but also a water
nanodroplet concentration gradient. Close to the NOP|water
interface, the size of the water nanodroplets will be the same as
those that are distant from the interface because the NOP|water
surface energy is the same in both cases. The shape of the
intersection of the two interfaces is described by the meniscus
of the NOP|water|glass system formed as the more dense water
molecules make contact with the hydrophilic glass surface near
the three-phase boundary. While we do not have a ready means
of evaluating the prole of the meniscus, the water forming the
meniscus may contribute to the eects we observe. Near the
NOP|glass interface, the water nanodroplet size is dierent for
the reasons discussed above, but due to the presence of a
meniscus, the total amount of water accessible to this interface
is not limited. Thus, there can be a relatively higher
concentration of large water droplets near the NOP|glass
interface, leading to a dielectric gradient that is m ore
pronounced than the gradient for the NOP|water interface,
and this is precisely the situation we observe experimentally
(Figures 9 and 10).
Taken collectively, the lifetime and anisotropy decay time
constant data indicate that there is an inltration of water into
NOP resulting from the presence of the NOP|water interface.
The water concentration gradient that exists normal to the
NOP|water interface is indicated by the uorescence lifetime
data, but there is not a gradient in the anisotropy decay data
indicating a size gradient. The nanoemulsion we observe
normal to the NOP|water interface is composed of a
distribution of water nanodroplets that maintain a constant

ASSOCIATED CONTENT

* Supporting Information
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Glass surface cleaning. Dependence of LRSC in NOP

uorescence lifetime and anisotropy decay time on distance
from the glass interface. Anisotropy decay curves as a function
of depth. Absorption spectra of LRSC. Time-resolved images of
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the partitioning of LRSC. This material is available free of

charge via the Internet at http://pubs.acs.org/.

AUTHOR INFORMATION

Corresponding Author

*E-mail: blanchard@chemistry.msu.edu.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We are grateful to the Donors of the Petroleum Research Fund
for their support of this work through grant 52692-ND6 and to
the National Science Foundation for their support of the
instrument construction through grant 1048548. We thank
Professor Xuefei Huang for the use of his DLS instrument. We
are grateful to Professor P. Krysinski and Professor S. Asher for
insightful discussions of these results.

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