Original Papers

A Fluorescence Microspectroscopic Study on the Diffusion Coefficient

of Rhodamine B in Single Cation-Exchange Resin Particles

Nguyen M. CUONG,*,# Shoji ISHIZAKA,**,***,****

and Noboru KITAMURA**,***,

Department of Chemistry, Graduate School of Science, Hokkaido University,

Sapporo 060-0810, Japan.

**

Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo

060-0810, Japan.

**** Department of Chemical Sciences and Engineering, Graduate School of

Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-0810,
Japan.
**** PRESTO, Japan Science and Technology Agency, Japan.

To whom correspondence should be addressed.

E-mail: kitamura@sci.hokudai.ac.jp

On leave from Institute of Marine Environment and Resources, 246 Danang Street,
Haiphong City, Vietnam.

Abstract

The intraparticle diffusion processes of a cationic dye (Rhodamine B, RB+) were in situ
studied for individual cation exchange resin microparticles (diameter = 14 - 16 m) by
means of confocal fluorescence microspectroscopy in special references to solution pH
effects on the diffusion coefficient of RB+. The intraparticle diffusion coefficients (D) of
RB+ were determined for both SO3H+- and SO3Na+-type cation-exchange resin
particles and we found the large pH dependence of the D value in the resin particles,
which was discussed in terms of both the acid-base equilibrium of RB+ and the Donnan
electric potential generated across the resin/water boundary.

Introduction

In 1996, we reported for the first time the direct observation of the intraparticle
diffusion processes of Rhodamine B (RB+) in single cation-exchange resin
microparticles on the basis of confocal fluorescence microspectroscopy.1 When
cation-exchange resin particles having SO3Na+ groups are soaked in an aqueous RB+
solution whose concentration is set below the ion-exchange capacity of the resin
particles used, all of the RB+ ions are adsorbed on the surface layers of the particles in
the initial stage of soaking. Under the conditions, since no RB+ is provided further from
the water phase to the particles, the intraparticle diffusion processes can be followed by
the time course of the fluorescence intensity profile of RB+ along the particle diameter
for an individual particle.1 In the initial stage of soaking, the RB+ fluorescence can be
observed from the surface layer of the particle and, thus, that from the upper and lower
parts of the particle along an excitation laser beam (z-axis) is observed as two
fluorescence peaks as shown later in detail (i.e., Fig. 3). Upon prolonged soaking, RB+
adsorbed in the surface layer of the particle diffuses into the particle interior, which
results in broadening of the fluorescence peaks. By analyzing such data, we evaluated
the diffusion coefficient of RB+ in the resin particle. In the case of a
styrene-divinylbenzene type cation-exchange resin having SO3Na+groups (CK08C,
cross-linking density 8%, Mitsubishi Chemicals Co. Ltd.), we showed that the time
necessary for homogeneous distribution of RB+ inside a single resin particle soaked in
an aqueous RB+ solution at pH = 7 was as long as 1 week and the diffusion coefficient
(D) of RB+ was D = (24) x 1013 cm2s1.1
On the other hand, we also reported that the diffusion coefficient of Malachite
Green (nonfluorescent cationic dye: MG+) in the CK08C resin was 8 x 1011 cm2 s1 (at

pH = 4) as determined by a laser trapping-microspectroscopy technique.2 The value was

much larger than the D value of RB+.1,2 In the previous paper, we reported that the
difference in the D value between RB+ and MG+ would be due to that in the solution pH
(pH = 7 for RB+ and pH = 4 for MG+), suggesting that pH effects on the dissociation
equilibria of both dyes and ion-exchange group of the resin governed strongly the
ion-exchange processes.2 In practice, the pKa value of RB+ has been reported to be 3.1 3.736 and RB+ undergoes the acid-base equilibrium as shown in Scheme 1,510 while
that of MG+ is 6.9.11,12 Since the D value of RB+(D(RB+)) in a CK08C resin particle has
been determined in an aqueous pH = 7 solution as described above, the small D(RB+)
value would be due to the participation of the zwitterionic form of Rhodamine B (RB)
to the ion-exchange processes at pH = 7. To clarify the implication of the acid-base
equilibria of RB+ and the ion-exchange group in the resin to D(RB+), the pH effects on
the D value is worth studying in detail.
In the present paper, we report pH effects on the D(RB+) values in SO3Na+ and
SO3H+ type cation-exchange resin particles and discuss the factors determining the
intraparticle diffusion processes in special references to the acid-base equilibrium of
RB+ and the Donnan electric potential difference between the resin and surrounding
water phases which is caused by a solution pH variation and the counter cation of the
ion-exchange group (i.e., SO3Na+ or SO3H+).

Experimental

Chemicals and Sample Preparation.

Rhodamine B (Tokyo Kasei, GR grade) was used as supplied, and pure water
(conductivity >17 M.cm) was obtained from a GSR-200 system (Advantec Toyo) or

Elix Advantage Water Purification System (M Millipore). A cation-exchange resin

(MCI-GEL, CK08S, Mitsubishi Chemicals Co. Ltd.), made of a divinylbenzene-styrene
copolymer (cross-linking density = 8%) having SO3Na+ groups, was used as an
ion-exchange material. The corresponding H+-type resin (abbreviated as CK08SH) was
prepared by repeated soaking of CK08S (1 g) in 100 mL of 2 mol/dm3 (= M) HCl
solution for 1 h to attain complete exchange of the counter ion. The resins were washed
thoroughly by deionized water and dried in air at room temperature. The pH of a RB+
solution was adjusted by adding a 0.1 M NaOH or HCl solution and was measured by
using a Horiba pH Meter D-51.
The present experimental procedures are as follows. The resin (CK08S or CK08SH,
2 mg) was soaked in 50 mL of an aqueous RB+ solution ([RB+] = 2 x 108M) at a given
pH value. Since the ion-exchange capacity of CK08S (9 x 106 equiv/2 mg of resin)1,2 is
much higher than the total mole number of RB+ in the water phase (~109 mol/50 ml of
solution) under the present conditions, RB+ is expected to adsorb on the surface layer of
each particle during the fast several minutes of soaking. The colloidal solution was then
poured onto a slide glass and covered with a cover slip as a sample, which was set on
the stage of a confocal fluorescence microscope described below. A single resin particle
was then selected in the solution and the fluorescence intensity profile of RB+ along the
particle diameter was recorded at a given soaking time.
Absorption and fluorescence spectra of RB+ in water were measured by using a
Hitachi U-3300 spectrophotometer and a Hitachi F-4500 spectrofluorometer,
respectively.
Confocal Fluorescence Microspectroscopy
A confocal fluorescence microspectroscopy system used in the present study is
shown schematically in Fig. 1. A 514.5-nm laser beam from an Ar+ laser (Innova 70,

Coherent) was used as an exciting light source. The laser beam whose intensity was
controlled by a neutral density filter was condensed by a lens and introduced to an
inverted optical microscope (Nikon, Eclipse E300) through a pinhole (P1, diameter =
100 m). The laser beam was reflected by a dichroic mirror (DM) and focused on a
single RB+/resin particle through an oil-immersion objective lens (magnification = 100,
numerical aperture = 1.30). The fluorescence from the particle was collected by the
same objective lens and imaged on a pinhole (P2, diameter = 80 m) in front of a
detector system: a cooled CCD detector (Andor Tech.) equipped with a polychromator
(1200 grooves/mm). The microscope stage was drove with steps of 0.25 - 1.0 m along
the laser beam axis to record the RB+ fluorescence intensity profile along the particle
diameter: z-axis. The spatial resolution along the z-axis was ca. 1 m.

Results and Discussion

pH Effects on the Absorption and Fluorescence Spectra of RB+

Before describing pH effects on D(RB+) in a resin particle, one should clarify the
acid-base equilibrium of RB+ in water. Figure 2 shows the pH dependences of the
absorption (a)) and fluorescence (b)) spectra of RB+ in the range of 2.50 < pH < 11.58.
RB+ showed the absorption maximum at around 554 nm and its spectral characteristics
were not sensitive to a pH variation. On going pH from 4.18 to 2.50, the absorbance at
around 554 nm slightly increased and the maximum wavelength was shifted slightly
from 554 to 557 nm. At pH > 4, the absorbance and the spectral band shape were almost
independent of pH. Reflecting such the pH dependence of the absorption spectrum, the
fluorescence spectrum at pH < 4 was shifted to the longer wavelength accompanying by
the decrease in the fluorescence intensity, while the spectrum was independent of the

solution pH above 4. On the basis of these spectral data, we evaluated the pKa value of
RB+ to be 3.4, which agreed very well with the reported values:3.1 - 3.7.36 At pH < pKa,
the main chemical species is the acid form (RB+), while that is the zwitterionic form of
Rhodamine B (RB) at pH > pKa. In the following sections, therefore, we discuss pH
effects of the D values on the basis of the acid-base equilibrium shown in Scheme 1.
Determination

of

the

value

RB+/RB

of

by

Confocal

Fluorescence

Microspectroscopy
Figure 3 shows a typical example of the time (t) course of the fluorescence intensity
profiles of RB+/RB along the diameter direction of a single CK08S cation-exchange
resin particle (diameter (d) 16 m) during soaking the particle in an aqueous RB+/RB
solution ([RB+/RB] = 2 x 108 M, the solution pH before soaking the particles, pHt=0 =
6.98). At t = 1 h (Fig. 3a), two fluorescence peaks were observed at around r = +8 and r
= 8 m, and almost no RB+/RB fluorescence could be detected from the center of the
particle (r = 0), indicating that RB+/RB adsorbed only on the surface layer of the
particle in the initial stage of soaking. Upon prolonged soaking as demonstrated in Fig.
3b, the fluorescence peaks at around r = 8 m broadened during 1 day (open circles)
and, at t = 5 days (closed circles), the fluorescence was observed from the entire volume
of the particle: homogeneous distribution of RB+/RB in the particle. The increase in the
fluorescence peak width with t corresponds to diffusion of RB+/RB into the particle
interior and, thus, the full-width at half-maximum (W1/2) of the fluorescence peak can be
used as a measure of the diffusion length of RB+/RB in the particle () as shown
schematically in Fig. 3a.
In the early stage of soaking, since one dimensional diffusion of RB+/RB from
the surface layer of the particle to the inner volume will be predominant, one can apply
the one dimensional diffusion equation, = (2Dt)1/2, where D is the diffusion coefficient

of RB+/RB: D(RB+/RB).1 The experiments analogous to those in Fig. 3 were

conducted for 9 ~ 11 single particles at given t and we plotted the average value
against t1/2. As the full data relevant to the experiments in Fig. 3 were displayed in Fig. 4,
we obtained a good linear relationship between and t1/2. In principle, the plot should
bisect the original point in Fig. 4. In practice, the data accumulated in a pH t=0 = 3
solution bisect the original point as shown in Fig. 4a. It is worth noting that, since the
spatial

resolution

along

the

z-axis

in

the

present

confocal

fluorescence

microspectroscopy system was ca. 1 m, we could not determine precisely the diffusion
length of RB+/RB shorter than 1 m. At pHt=0 = 7.0 as shown in Fig. 4a, diffusion of
RB+/RB in the resin particle was very slow compared with that at pH t=0 = 3 (Fig. 4a)
and the plot did not bisect the original point. Therefore, the D value estimated from the
slope value in Fig. 4b is erroneous: D(RB+/RB) =1.6 x 1013 cm2s1 at pHt=0 = 7.0.
Nonetheless, the D value was in good agreement with that reported previously: (24) x
1013 cm2s1at pHt=0 ~ 7.1 It is worth noting that the reported value determined by
confocal

fluorescence

microspectroscopy

has

been

checked

also

by

laser

trapping-absorption microspectroscopy and, the D values determined by the two

methods have been agreed with one another: see ref. 1 in details. Therefore, we suppose
that the D value determined by confocal fluorescence microspectroscopy in the present
study at pHt=0 > 7.0 is also meaningful.
According to the acid-base equilibrium shown in Scheme 1 and Fig. 2, since
Rhodamine B takes the zwitterionic form at pH = 7, the D value determined at pH = 7 is
concluded to be that of RB: D(RB) = 1.6 x 1013 cm2s1. Clearly, the small diffusion
coefficient of RB+/RB compared to that of MG+ observed at around pH ~ 7 is due to
the diffusion coefficient of the zwitterionic form of Rhodamine B.

Solution pH Effects on the D values of RB+/RB in Na+-type and H+-type Cation

Exchange Resin Microparticles
Analogous experiments with those in Figs.3 and 4 can provide the D(RB+/RB)
value under given conditions. Solution pH effects on D(RB+/RB) thus obtained for the
Na+-type resin particles are summarized in Fig.5 and Table 1. As seen in the figure, the
D value was almost constant at 1 x 1013 cm2s1 at pHt=0 > 7, while that increased with
lowering the solution pH. In particular, the D value increased very sharply at pHt=0 < 4
and was 2.8 x 1011 cm2s1 at pHt=0 = 2.54, which was 280 times larger than that at pHt=0
7. At pHt=0 7, since Rhodamine B takes the zwitterionic form (RB) as mentioned
above, the D value is very small and constant irrespective of the solution pH. At 4 <
pHt=0 < 7, a decrease in the pH value gives rise to an increase in the contribution of the
cationic form (RB+) to the total RB+/RB concentration, leading to the moderate
increase in D with a decrease in pH. At pHt=0 < pKa = 3.4, although the main chemical
species contributing to intraparticle diffusion should be RB+, the D value increases
sharply with a decrease in pH. The D value of RB+(D(RB+)) in the Na+-type
cation-exchange resin was estimated to be 2.8 x 1011 cm2 s1 at pHt=0 = 2.54, which was
comparable to that of Malachite Green determined for the similar cation-exchange resin
particles: 8 x 1011 cm2s1.2
Figure 6 shows the pH dependence of D(RB+/RB) in the H+-type
cation-exchange resin particles (CK08SH), whose source is the essentially the same
with the experiments shown in Fig.4: CK08S (see also Table 1). If one compares the
data in Fig.5 (Na+-type resin) with those of Fig.6 (H+-type resin), the pH dependence of
D(RB+/RB) observed for the H+-type resin shifts to the high pH region compared to
that for the Na+-type resin. It is worth noting that, in both cases, the D values are plotted
against pHt=0. When H+-type resin particles are soaked in an aqueous RB+/RB solution,

the solution becomes more acidic. At pHt=0 = 6.75, as an example, the solution pH
lowered quickly during first 5 minutes after soaking and gradually reached at a constant
value (pHt= = 4.82, pH = pHt=0 - pHt= = 1.93) owning to H+ release from the resin
phase to the water phase. Therefore, the pH effects on the acid-base equilibrium of
RB+/RB are different between the H+- and Na+-type resin particle systems and, thus,
the pH dependences of D(RB+/RB) in Figs.5 and 6 cannot be compared directly on the
basis of pHt=0. To discuss the pH effects on the D value between the two systems, we
plotted the D value determined for the H+-type resin particles against pHt= as the
results were shown in Fig.7. By plotting D(RB+/RB) against pHt=, the pH dependence
curve was shifted to the more acidic side. Nonetheless, the absolute D value at a given
pH value was larger in the H+-type resin particles compared with that in the Na+-type
resin particles. Typically, the D values in the H+-type resin particles at pHt= = 2.14,
4.38, and 5.64 were 5.29 x 1011, 4.09 x 1011 and 0.06 x 1011 cm2s1, respectively,
while those in the Na+-type resin particles at pHt=0 = 2.54, 4.08, and 5.03 were 2.84 x
1011, 0.11 x 1011, and 0.06 x 1011 cm2s1, respectively. Since it has been reported that
the mobility of H+ in a cationic exchange resin is faster than that of Na+, this will be
reflected on the D values of RB+/RB.13 Furthermore, since the SO3H+group in a
cation-exchange resin is reported to be more hydrated compared to the SO3Na+
group,13,14 the electrostatic interaction between H+ and the SO3 group should be weaker
and this should give rise to the faster ion-exchange reaction between the ion-exchange
group and RB+/RB in the H+-type resin compared to that in the Na+-type resin.
Another factor governing the pH and counter cation (H+ or Na+) effects on the D
value would be the Donnan potential difference generated across the particle/water
boundary, which has been frequently discussed as the factor determining ion-exchange
processes.1521 When the H+-type resin particles are soaked in a given pH solution, the

10

solution pH becomes more acidic as mentioned before. Thus, H+ released from the fixed
SO3charge in the resin to the water phase should generate a membrane potential
across the resin particle/water boundary: Donnan potential difference. The Donnan
potential difference () is given as in Eq. (1), 1521
i o

RT [Ci ]
ln
F
[Co ]

(1)

where i and o are the electrical potentials in the resin and water phases, respectively. R,
T, and F are the usual meanings and, Ci and Co are the mobile ion (i.e., H+)
concentrations in the resin and water phases, respectively. Equation (1) indicates that the
larger is the mobile ion concentration difference between the two phases, the higher is
. In the present case, H+ release from the resin phase to the water phase gives rise to
generation of the negative electrical potential across the interface, which should
suppress diffusion of the cationic dye, RB+/RB, into the particle interior. By lowering
the solution pH (i.e., pHt=0) from 7 to 2, as an example, the amount of H + released from
the particle phase to the water phase should become lower and, thus, the value
should become smaller, leading to the increase in the D value. In the case of the
experiments in Fig.6 or 7, pH (= pHt=0 pHt=) at pHt=0 = 6.75 and 2.16 were 1.93 and
0.02, respectively. These discussions and experimental results indicate that the value
governs the D value of RB+/RB in addition to the acid-base equilibrium of RB+/RB
discussed in the preceding section for the Na+-type resin particles.

Conclusions

We succeeded in determining the diffusion coefficients of Rhodamine B in single cation

exchange resin microparticles on the basis of a confocal fluorescence microspectrocopy

11

technique and studied the solution pH effects on the D(RB+/RB) value. The
D(RB+/RB) values showed large pH dependences for both SO3Na+- (CK08S) and
SO3H+-type (CK08SH) resin particles. In the case of CK08S, the D(RB+/RB) value
varied from 1.56 x 10-13 to 284 x 10-13 cm2s1 on going from pHt=0 = 6.98 to 2.54 while
that in CK08SH increased from 119 x 10 -13 cm2 s1 at pHt=0 = 6.75 to 529 x 10-13 cm2s1
at pHt=0 = 2.16. Knowing the pKa value of RB+/RB to be pH ~ 3.4, the moderate pH
dependence of the D value in the pHt=0 range of 3 < pH < 7 was discussed in terms of
the acid-base equilibrium of the dye, while that at pHt=0 < 3.4 (~pKa) was explained by
the Donnan electric potential generated across the resin/water boundary. Since the
negative Donnan electric potential preventing diffusion of RB + to the resin interior
becomes lower with decreasing the solution pH, the D value becomes higher at a high
acidic solution. Furthermore, the diffusion coefficient of RB+ in the H+-type resin was
found to be larger than that in the Na+-type resin, demonstrating faster mobility of H+ in
the resin than that of Na+.

Acknowledgements

N. K. is grateful for a Grant-in-Aid from the Ministry of Education, Culture, Sports,

Science and Technology, Japan (No. 23245015B01) for partial support of the research.

12

References

1.

H.-B. Kim, M. Hayashi, K. Nakatani, N. Kitamura, K. Sasaki, J. Hotta, and H.

Masuhara, Anal. Chem., 1996, 68, 409 (correction: Anal. Chem. 1996, 68, 1987).

2.

H.-B. Kim, S. Habuchi, M. Hayashi, and N. Kitamura, Anal. Chem., 1998, 70, 105.

3.

S. Woislawski, J. Am. Chem. Soc., 1953, 75, 5201.

4.

R.W. Ramette and E.B. Sandell, J. Am. Chem. Soc., 1956, 78, 4872.

5.

I. L. Arbeloa and P. R. Ojeda, Chem. Phy. Lett., 1981, 79, 347

6.

P. J. Sadkowsky and G.R. Fleming, Chem. Phys. Lett., 1978, 57, 526.

7.

I. L. Arbeola and K.K. Rohatgi-Mukherjee, Chem. Phys. Lett., 1986, 129, 607.

8.

A. A. El-Rayyes, A., Al-Betar, T. Htun, and U. K. A. Klein, Chem. Phys. Lett., 2005,
414, 287.

9.

J. Ferguson and A. W.-H. Mau, Chem. Phy. Lett., 1972, 17, 543.

10. J. Ferguson and A. W.-H. Mau, Aust. J. Chem., 1973, 26, 1617.
11. S. J. Culp and F. A. Beland, J. Am. Coll. Toxicol., 1996, 15, 219
12. C. Long, Z. Mai, B. Zhu, X. Zou, Y. Gao, and X. Huang, J. Chromatogr. A, 2008,
1203, 21
13. G. E. Boyd and B. A. Soldano, J. Am. Chem. Soc., 1953, 75, 6091.
14. A. A. Zagorodni, Ion Exchange Materials - Properties and Applications, 2007,
Elsevier, Oxford OX5 1GB, UK.
15. K. Nomura, Bull. Chem. Soc. Jpn., 1996, 69, 2533.
16. M. L. Jansen, G. W. Hofland, J. Houwers, A. J. J. Straathof, L. A. M. van der
Wielen, K. C. A. M. Luyben, and W. J. J. van den Tweel, AIChE J., 1996, 42,
1925.
17. H. Yao, Y. Takada, and N. Kitamura, Langmuir, 1998, 14, 595.

13

18. P. Ramrez, A. Alcaraz, S. Maf, and J. Pellicer, J. Colloid Interface Sci., 2002, 253,
171.
19. H. Shen and D. D. Frey, J. Chromatogr. A, 2004, 1034, 55.
20. C. A. Burns, J.-F. Boily, R. J. Crawford, and I. H. Harding, J. Coolid Interface Sci.,
2004, 278, 291.
21. O. V. Bobreshova, A. V. Parshina, K. A. Polumestnaya, N. G. Dyachkova, and L.
A. Zagorodnykh, Russ. J. Electrochem., 2007, 43, 1321.

14

Table 1. Effects of pH on the Diffusion coefficients of RB+/RB in the CK08S and

CK08SH resin microparticles.
CK08Sa
pH

D x 1013 cm2s-1

2.54

CK08SHb
pHt=0c

pHt=d

D x 1013 cm2s-1

284.90 9.40

2.16

2.14

529.00 17.46

2.95

141.00 4.65

3.06

3.04

475.00 15.68

3.15

74.50 2.46

3.9

3.87

444.00 14.65

4.08

10.89 0.36

5.4

4.38

409.00 13.50

5.03

6.22 0.21

6.75

4.82

119.00 3.93

6.11

3.30 0.11

8.02

5.08

51.00 1.68

6.98

1.56 0.05

9.13

5.64

6.00 0.20

8.2

1.36 0.04

9.82

6.38

1.91 0.06

9.78

0.96 0.03

10.02

7.54

1.52 0.05

10.15

8.65

1.41 0.05

10.25

9.85

1.32 0.04

Na+-type counter-ion resin.

H+-type counter-ion resin.

initial solution pH before soaking the resin particles.

solution pH after soaking the resin particles.

15

Figure captions

Scheme 1. Acid-base equilibrium of RB+/RB.

Figure 1

Optical setup of a confocal fluorescence microspectroscopy system (P1, P2:

Pinhole; DM: dichroic mirror).

Figure 2.

Effects of pH on the absorption (a)) and fluorescence (b)) spectra of

RB+/RB in the pH range of 2.50 < pH < 11.53: [RB+/RB] = 106 M.

Figure 3.

Fluorescence inetensity profile of RB+/RB along the particle diameter of a

CK08S (d16 m) resin particle after 1 h (a)) , 1 day (), and 5days () (b))
soaking of the particle in an aqueous RB+/RB solution: [RB+/RB] = 2 x
108 M, pH = 7.0.

Figure 4.

Relationships between and t1/2 determined for single CK08S resin

+
microparticles
(d ~ 16 m) soaked in an aqueous RB
/ RB solution
4.0
6
demo

demo

demo

demo

demo

demo

demo

demo

demo
d e+ m o
Effects of pH on the diffusion coefficient D of RB+/RB2.5 in
the Na
-type d e m o

demo

demo

demo

demo

demo

8
5
([RB+/RB
] = 2 xd 10
M)d eat
pH d=e m3 o(a)) and pH = 7 (b)).
demo
emo
mo

3.5

/ m

Figure 5.

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

+ 1.0
+
mo
demo
demo
demo
Effects 1ofd epH
H
t=0 on the diffusion coefficient D of RB /RB d in
e m the
o
d e -type
mo
demo

demo

resin particles. Inset is the pH dependence of log D.

2

Figure 6.

/ m

3.0

demo

demo

demo

demo

0
0.0
2.5
5.0
7.5
10.0
12.5
15.0
17.5
20.0
22.5
resin particles.
Inset
is
the
pH
t=0 effects on log D.
1/2

Time / min

1/2

2.0
1.5

0.5
0.0
0

demo
10

demo
20

30

demo
40
1/2

50

Time / min

Figure 7.

Effect of pHt= on the diffusion coefficient D of RB+/RB in the H+-type

resin particles. Inset is the pHt= dependence of log D.

16

1/2

demo
60

70

80

Cl

H 3C
H 3C

(RB+ )

CH3

COOH

Scheme 1.

CH3

pH > pKa

H 3C
H 3C

COO

17

CH3

(RB )

pH < pKa

Acid-base equilibrium of RB+/RB.

CH3

Figure 1 Optical setup of a confocal fluorescence microspectroscopy system (P1, P2:

Pinhole; DM: dichroic mirror).

18

a)

0.12

pH 2.50
pH 3.10
pH 3.60
pH 4.18
pH 5.75
pH 7.47
pH 9.49
pH 11.58

Absorbance

0.10
0.08
0.06
0.04
0.02
0.00
450

500

550

600

650

Wavelength / nm

Fluorescence intensity (arb.)

b)

540

pH 2.50
pH 3.10
pH 3.60
pH 4.18
pH 5.75
pH 7.47
pH 9.49
pH 11.58

560

580

600

620

640

660

680

Wavelength / nm

Figure 2 Effects of pH on the absorption (a)) and fluorescence (b)) spectra of RB+/RB
in the pH range of 2.50 < pH < 11.53: [RB+/RB] = 106 M.

19

Laser beam
(Z axis)

a)

+12
+8

W1/2

r / m

+4

0
-4
-8
-12
0.0

0.2

0.4

0.6

0.8

1.0

Normalized fluorescence intensity

b)

+12
+8

r / m

+4

0
-4
-8
-12
0.0

0.2

0.4

0.6

0.8

1.0

Normalized fluorescence intensity

Figure 3 Fluorescence inetensity profile of RB+/RB along the particle diameter of a

CK08S (d16 m) resin particle after 1 h (a)) , 1 day (), and 5days () (b)) soaking of
the particle in an aqueous RB+/RB solution: [RB+/RB] = 2 x 108 M, pH = 7.0.

20

a)
5

/ m

4
3
2
1
0

10

Time

15

1/2

/ min

20

1/2

b)

/ m

20

40
1/2

Time

60

/ min

80

1/2

Figure 4 Relationships between and t1/2 determined for single CK08S resin
+
microparticles (d ~ 616 m) soaked in an aqueous RB+/ RB solution ([RB
/RB] = 2 x
4.0
demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

21
demo

demo

demo

demo

demo

demo

demo

demo

demo

1.0

demo

demo

demo

demo

0.5

5
108 M) at pH = 3 (a))
and pHd e=m 7o (b)).
demo
demo

demo

3.5

demo
3.0

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

2.5
3

/ m

/ m

demo

2.0
1.5

a
-10

11

2 -1

log D / cm s

D x 10 / cm s

2 -1

3.0
2.5
2.0

-11

-12

-13

1.5

10

pH

1.0
0.5
0.0
2

10

pH

Figure 5.Effects of pH on the diffusion coefficient D of RB+/RB in the Na+-type resin

particles. Inset is the pH dependence of log D.

22

a
6

-10

11

2 -1

log D / cm s

D x 10 / cm s

2 -1

5
4

-11

-12

-13
2

10

pHt = 0

2
1
0
1

10

11

pHt = 0
Figure 6 Effects of pHt=0 on the diffusion coefficient D of RB+/RB in the H+-type resin
particles. Inset is the pHt=0 effects on log D.

23

6
-10

11

2 -1

log D / cm s

D x 10 / cm s

2 -1

5
4

-11

-12

-13

10

pHt =

2
1
0
2

pHt =

10

Figure 7 Effect of pHt= on the diffusion coefficient D of RB+/RB in the H+-type resin

particles. Inset is the pHt= dependence of log D.

4.0
3.5
3.0

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

demo

/ m

2.5
2.0
1.5
1.0
0.5
0.0
0

demo
10

demo
20

30

demo
40
1/2

50

Time / min

24

1/2

demo
60

70

80