Volumetric, conductometric and uorescence probe studies of interactions

between glycyl dipeptides and sodium caprylate in aqueous media

Zhenning Yan
a,
, Xiaolan Wang
a
, Xiangru Bai
a
, Shuangqiang Wang
a
, Jianji Wang
b
a
Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450052, PR China
b
School of Chemistry and Environmental Science, Henan Normal University, Xinxiang, Henan 453007, PR China
a r t i c l e i n f o
Article history:
Available online 6 February 2012
Keywords:
Glycyl dipeptide
Sodium caprylate
Density
Conductivity
Fluorescence spectra
a b s t r a c t
The interactions of glycyl dipeptides (glycylglycine, glycyl-L-valine and glycyl-L-leucine) with sodium
caprylate (NaC
8
) in aqueous solution have been investigated by a combination of density, conductivity
and uorescence methods. Apparent molar volumes (V
2,/
), standard partial molar volumes (V

2;/
), and
standard partial molar volumes of transfer from water to aqueous NaC
8
solutions (D
t
V
o
) are evaluated
using density data. The limiting molar conductivity of sodium caprylate (K
o
) and its anion contribution
k
o
(C

8
), as well as the Stokes radii of caprylate anion in aqueous glycyl dipeptide solutions have been cal-
culated using conductivity data. Pyrene uorescence spectra were used to estimate the critical micellar
concentration (c
cmc
) of NaC
8
in aqueous dipeptide solutions. The analysis shows that the interactions
of sodium caprylate with charged and polar groups of glycyl dipeptides are dominating over the sodium
caprylate-non-polar group interactions over the entire concentration range of sodium caprylate. From the
volumetric data, it is suggested that the glycyl dipeptides are solubilized in the palisade layer of sodium
caprylate micelles. The decrease in K
o
values of sodium caprylate with an increase in dipeptide concen-
tration is attributed to the interaction of sodium caprylate with the dipeptides and increasing viscosity of
solvent. The addition of dipeptide in water decreases the c
cmc
of NaC
8
. The interactions of glycyl dipep-
tides with sodium caprylate increase with the increase in the size of side chain of carboxylate anions
and of glycyl dipeptides.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
Electrolyte solutions are of fundamental importance to chemis-
try and biology as they form a basic matrix for technological uids
and the evolution and function of life. Studies on various thermo-
dynamic properties of amino acids and simple peptides in aqueous
solutions of electrolyte have attracted increasing interest due to
their importance in the better understanding of the nature and
mechanisms taking place in biological cells [1]. Carboxylate salts
are the organic electrolytes which have signicant biological and
industrial importance. Some workers [217] have investigated
the effect of carboxylate salts on the physico-chemical properties
of amino acids and peptides. Among them, there are works carried
out in our laboratory. Comparison of results in these studies has
shown that the size and nature of carboxylate anion, the nature
of metal ion modulate the interactions between carboxylate anion
and the amino acids or peptides. These results are very useful for
obtaining information about various types of interactions occur-
ring in these solutions. Studying these interactions can provide
important insight into the conformational stability and unfolding
behavior of globular proteins. In these studies, the chosen carbox-
ylate salts are sodium acetate, magnesium acetate, calcium acetate
and sodium butyrate which have short alkyl chain. In a previous
study [18], it has been shown that if the large-size anions were
introduced into the solution, the protein acquires the A state,
which has been proposed as an important intermediate form,
and could be a key step in understanding the protein folding prob-
lem. However, few studies [8,12,14,17] on the thermodynamic
properties of amino acids or peptides have been carried out in
aqueous solutions of sodium carboxylate with long alkyl chain.
Sodium caprylate (NaC
8
) is a surfactant, and is known to inhibit
the DNA synthesis and to release cytoplasmic protein inducing
brolast damage [19]. Recently we have investigated ve dipeptides
with different structures in mixed aqueous sodium carboxylate
solution in a wide range of concentrations of the co-solvent [13
17]. According to our knowledge, the interactions between dipep-
tides with NaC
8
have never been determined before. Therefore, it
is interesting to investigate the behavior of some dipeptides in
micellar solutions of sodium caprylate. Dipeptides have been
chosen because they are among the building units of complex bio-
molecules such as proteins. They are also important biological mol-
ecules due to their wide range of applications in drug production
0021-9614/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jct.2012.01.024

Corresponding author. Tel.: +86 13643710678; fax: +86 371 67761744.

E-mail address: yanzzn@zzu.edu.cn (Z. Yan).
J. Chem. Thermodynamics 52 (2012) 8994
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J. Chem. Thermodynamics
j our nal homepage: www. el sevi er . com/ l ocat e/ j ct
hinged on to their ability to act as hormones and for their role as sig-
nal transmittance [20]. The systematic study of peptides can pro-
vide valuable information about their behavior in solutions. In
continuation of our studies on physico-chemical properties of
peptides, in the present paper, we report the interactions of sodium
caprylate (NaC
8
) with glycyl dipeptides (2-[(2-aminoace-
tyl)amino]acetic acid (commonly known as glycylglycine), 2-[(2-
aminoacetyl)amino]-3-methylbutanoic acid (common name
glycyl-L-valine), and (2S)-2-[(2-aminoacetyl)amino]-4-methylpen-
tanoic acid (commonly known as glycyl-L-leucine)) by densimetry,
conductometry and uorescence spectroscopy.
2. Experimental
2.1. Chemicals
All of the used dipeptides 2-[(2-aminoacetyl)amino]acetic acid
(commonly known as glycylglycine with CAS # 556-50-3),
2-[(2-aminoacetyl)-amino]-3-methylbutanoic acid (with CAS #
1963-21-9 and common name glycyl-L-valine) and (2S)-2-[(2-
aminoacetyl)amino]-4-methylpentanoic acid (commonly known
as glycyl-L-leucine with CAS #869-19-2) were supplied by Sigma
with a mass fraction purity of 0.990. Each sample was re-crystal-
lized twice fromaqueous ethanol solutions and dried for 24 h under
vacuumat roomtemperature. They were then stored over P
2
O
5
in a
desiccator before use. Analytical reagent grade sodium caprylate
(Shanghai Chem. Co.) was twice re-crystallized from aqueous etha-
nol solutions and dried under vacuumat T = 383 Kfor two days. Pyr-
ene (mass fraction purity P0.990, Sigma) was used without further
purication. Potassium chloride (mass fraction purity of 0.99999,
Aldrich Chem. Co.) was dried for 48 h at T = 373 K and was used to
determine the conductance cell constant. The details of the com-
pounds used in the work are also given in table 1. Water with a con-
ductivity of (0.8 to 1.0) 10
4
S m
1
was obtained by distilling
deionised water. In densimetry, all of the solutions were prepared
gravimetrically with a Shimadzu AY 120 balance with an uncer-
tainty of 0.1 mg. The uncertainty in molality was
0.0002 mol kg
1
. In the conductometric experiment, all of the
mass determinations were done on a Satorius BP 211D digital bal-
ance having an uncertainty of 0.01 mg, and the molalities calcu-
lated found to be uncertain to 0.00002 mol kg.
2.2. Apparatus and procedures
Solution densities were measured to 1 10
3
kg m
3
with an
Anton Paar DMA 60/602 vibrating-tube digital densimeter that was
calibrated daily at T = 298.15 K using dry air and water with a con-
ductivity of (0.8 to 1.0) 10
4
S m
1
. A linear relation between the
density of the uid and the square of the vibrating period
(q = a(s
2
b)) was assumed. The reproducibility and the uncer-
tainty in density measurement were found to be 3 10
3
kg m
3
and 1 10
2
kg m
3
. The temperature control of the densimeter
was made with Schott thermostat units, which have a thermal sta-
bility of 0.005 K.
The electrical conductivity of each sample was measured with a
conductivity meter (Model 145A+, Thermo Orion), using a conduc-
tivity cell (Model 011510, Thermo Orion). The conductance cell
was equipped with a water circulating jacket, and the temperature
was controlled within 0.02 K with a low temperature thermostat
(Model DC-2006, Shanghai Hengping Instrument Factory). The cell
constant was calculated by repeated measurements of KCl solu-
tions. The uncertainty of the conductivity measurements was esti-
mated to 0.5%. All data were corrected with specic conductivity
of the solvent.
Fluorescence spectra were recorded on a F4500 Hitachi uores-
cence spectrometer at T = 298.15 K using emission and excitation
slit widths of 2.5 and 5 nm, respectively, with a scan rate of
60 nm min
1
. All systems were examined in a solution of
1.0 10
7
mol dm
3
pyrene used as a probe. The excitation wave-
length was 335 nm. The molality of dipeptides was (0.01, 0.025,
and 0.04) mol kg
1
.
3. Results and discussion
3.1. Volumetric property of glycyl dipeptide
The density data measured for the (glycyl dipeptides + sodium
caprylate + water) ternary systems at T = 298.15 K are given in ta-
ble S1 of table S1 of supplementary material as a function of molal-
ity of glycyl dipeptides (m
p
) and of sodium caprylate (m
NaC8
).
Apparent molar volumes, V
2,/
, of glycyl dipeptides were calculated
from the solution densities, q, using the equation
V
2;/
= M=q (q q
o
)=m
p
qq
o
; (1)
where Mis the molar mass of glycyl dipeptideds and q
o
is the density
of aqueous sodium caprylate solutions. Calculated apparent molar
volumes for glycyl dipeptideds are also listed in table S1. The uncer-
tainty in the determination of V
2,/
occurring because of the measure-
ment of various quantities has been calculated. The uncertainty
values for the V
2,/
range from(0.009 to 0.14) cm
3
mol
1
for the low-
er (60.02 mol kg
1
) and higher concentration ranges for dipeptides,
respectively. The reported apparent molar volume data for the
dipeptides were found to be adequately presented by the linear
equation
V
2;/
= V

2;/
S
V
m
p
; (2)
where V

2;/
is the innite dilution apparent molar volume that
equals the standard partial molar volume, and S
V
is an experimen-
tally determined parameter. Values of V

2;/
have been evaluated by
weighted least-square regression analysis. The standard partial
molar volumes for the glycyl dipeptides in aqueous solutions of
(0.4, 0.6, 0.8, and 1.0) mol kg
1
sodium caprylate are represented
in table 2 along with their standard deviations.
It is known that solutesolute interactions at innite dilution
are absent, therefore, the values of V

2;/
provide information
TABLE 1
Specication of chemical samples.
Chemical name Source Initial mass fraction purity Purication method Final mass fraction purity Analysis method
Glycylglycine Sigma 0.990 Recrystallization 0.992 HPLC
a
Glycyl-L-valine Sigma 0.990 Recrystallization 0.995 HPLC
a
Glycyl-L-leucine Sigma 0.990 Recrystallization 0.993 HPLC
a
Sodium caprylate Shanghai Chem. Co. 0.97 Recrystallization 0.978 NMR
b
Pyrene Sigma P0.990
Potassium chloride Aldrich 0.99999
a
High pressure liquid chromatography.
b 1
H and
13
C NMR.
90 Z. Yan et al. / J. Chem. Thermodynamics 52 (2012) 8994
regarding solutesolvent interaction. The V

2;/
values given in table
2 are positive and increase with an increase in concentration of so-
dium caprylate for three studied glycyl dipeptides, thereby show-
ing the presence of strong solutesolvent interactions. In general,
the interactions between the glycyl dipeptides and sodium capry-
late can be classied into: (a) ionion interactions between Na
+
/
carboxylate ion of sodium caprylate with the COO

=NH

3
group
of glycyl dipeptides, respectively; (b) ionpeptide group interac-
tions between ions of sodium caprylate and the peptide backbone
unit (CH
2
CONH) of dipeptides; (c) ionnon-polar group interac-
tions between the ions of sodium caprylate and the hydrophobic
side chain of dipeptide, and (d) non-polarnon-polar group inter-
actions between the hydrophobic side chains of dipeptide and
those of the salts. According to the co-sphere overlap model [21]
the effect of overlap of hydration co-sphere is destructive. Mishra
et al. [22] using this model observed that the overlap of co-sphere
of two ionic species shows an increase in volume, whereas the
overlap of hydrophobichydrophobic groups and ionhydrophobic
groups results in net decrease in volume. Thus, in the light of the
above fact, the observed positive V

2;/
values explain that the inter-
action contributions of types (a) and (b) are stronger than those of
types (c) and (d). Further, it is seen from table 2, that the V

2;/
val-
ues are in sequence of glycylglycine < glycylvaline < glycylleucine,
which is also the order of the size of the side chain (hydrophobic
group) in the glycyl dipeptides, i.e. the increase on V

2;/
may be
attributed to the increased hydrophobic/non-polar character of
the side chain of these glycyl dipeptides causing a reduction in
electrostriction at the terminal charged groups [23].
The standard partial molar volumes of transfer for the glycyl
dipeptides from water to aqueous solutions of sodium caprylate
were calculated by
D
t
V

= V

2;/
(in aqueous NaC
8
) V

2;/
(in water); (3)
where V

2;/
(in water) is the standard partial molar volume for glycyl
dipeptides in water and is taken from our earlier publication [13].
The calculated results are presented in table 3. As seen from table
3, D
t
V values of glycyl dipeptides are positive and increase with
increasing concentration of NaC
8
. The positive D
t
V values can be
explained on the basis that sodium caprylate interacts directly
through electrostatic interactions with the zwitterionic end group
and peptide backbone unit of the glycyl dipeptides, thereby leading
to a volumetric reduction in their electrostriction of the solvent and
a positive partial molar volume of transfer. With increasing sodium
caprylate concentration, this interaction will become stronger and
therefore D
t
V increases.
Using values of V

2;/
for the glycyl dipeptides in 1.0 mol kg
1
aqueous sodium acetate [13], sodium butyrate [15], sodium capro-
ate [14] and sodium caprylate solutions at T = 298.15 K, we plotted
V

2;/
values for the glycyl dipeptides against the number of carbon
atoms (n
s
) in hydrocarbon chain of carboxylate anion in gure 1a
(taking glycylglycine as example). It is obvious that the values of
V

2;/
for a given glycyl dipeptide in short chain sodium carboxylate
solutions (NaC
2
, NaC
4
and NaC
6
) increase gradually with increasing
side chain length of the carboxylate anion. However, there is an
exception to V

2;/
(in NaC
8
). These values in aqueous NaC
8
solutions
are much larger than the corresponding values in other salt solu-
tions. Further, from the comparison of D
t
V values of the glycyl
dipeptides in different sodium carboxylate solutions, it is found
that at a given solvent concentration (say 1.0 mol kg
1
), D
t
V (in
NaC
8
) are also much larger than those in aqueous NaC
2
, NaC
4
and
NaC
6
solutions (gure 1b, taking glycylglycine as example). All of
these indicated that the interactions of the glycyl dipeptides with
NaC
8
are different from those with NaC
2
, NaC
4
and NaC
6
. Previous
study showed that micelles are formed in aqueous NaC
8
, and its
critical micellar concentration is found to be about 0.35 mol dm
3
in water at T = 298.15 K [24]. The aqueous sodium caprylate solu-
tions studied here are micellar solutions. Vikingstad [25,26] inves-
tigated the partial molar volumes of n-alcohols, n-diols, sodium
alkylcarboxylates and disodium-alkyldicarboxylates in micellar
solutions of sodium alkylcarboxylate (NaC
8
- NaC
12
). He found
that the partial molar volumes of these compounds in micellar
solutions are much larger than those in aqueous solution. This
clearly indicates a hydrocarbon surrounding for these polar mole-
cules in the micellar solutions. It is now generally accepted that
more polar solutes tend to be solubilized in the palisade layer of
the micelle. In our previous study [27] the standard partial molar
volume for a-amino acids in aqueous sodium carboxylate solutions
also exhibits the same behavior as the studied glycyl dipeptides in
this paper. Since the structure of peptide is similar to that of amino
acid, as polar molecules, some portions of the glycyl dipeptides are
probably solubilized in the palisade layer of the micelle. So there
exist the interactions of the glycyl dipeptides with not only ions
but also micellar molecules of sodium caprylate. These lead to
the stronger interactions of sodium caprylate with glycyl dipep-
tides than those of sodium acetate, sodium butyrate and sodium
caproate. These interactions give rise to the larger increase in
V

2;/
and D
t
V of glycyl dipeptides in micellar solution of sodium
caprylate.
3.2. Conductometric properties of sodium caprylate
The conductance data (K) of sodium caprylate in aqueous and
aqueous dipeptide solutions of (0.05, 0.1, 0.15, and 0.2) mol kg
1
are listed in table S2 of the supplementary material. The limiting
molar conductivity (K
o
) of NaC
8
was obtained by least squares t-
ting the experimental data in table S2 to the expression [28]
K = K
o
A

c
NaC
8
p
=(1 B

c
NaC
8
p
); (4)
where K
o
, A and B are tting parameters, c
NaC8
is the molarity of
NaC
8
and was obtained by converting from molality with the den-
sity. The limiting molar conductivities obtained are given in table
4. The corresponding value obtained in aqueous solution is also gi-
ven in table 4 for comparison. The excellent agreement between the
obtained K
o
value in this work and the value in reference [29] is
noted.
Table 4 shows that the K
o
values for NaC
8
decrease with an in-
crease of peptide content and are very low as compared with those
in water. This can be ascribed to the facts that (i) with the increase
in microscopic viscosity of the mixtures, the mobility of ions de-
creases, and (ii) with the increase in peptide content of mixtures,
TABLE 2
Standard partial molar volumes (V

2;/
) for the glycyl dipeptides in aqueous sodium
caprylate solutions at T = 298.15 K.
m
NaC8 V
2;/
=(cm
3
mol
1
)
0.4 mol kg
1
0.6 mol kg
1
0.8 mol kg
1
1.0 mol kg
1
Glycylglycine 82.75 0.08 86.21 0.06 87.55 0.08 88.08 0.08
Glycylvaline 128.03 0.02 132.17 0.11 133.35 0.10 133.62 0.08
Glycylleucine 145.97 0.02 150.39 0.05 152.05 0.08 153.40 0.07
TABLE 3
Standard volumes of transfer (D
t
V
o
) for the glycyl dipeptides from water to aqueous
sodium caprylate solutions at T = 298.15 K.
m
NaC8
D
t
V
o
/(cm
3
mol
1
)
0.4 mol kg
1
0.6 mol kg
-1
0.8 mol kg
1
1.0 mol kg
1
Glycylglycine 6.46 0.11 9.92 0.09 11.26 0.11 11.79 0.11
Glycylvaline 5.78 0.05 9.92 0.12 11.10 0.11 11.37 0.09
Glycylleucine 6.28 0.10 10.70 0.11 12.36 0.13 13.71 0.12
Z. Yan et al. / J. Chem. Thermodynamics 52 (2012) 8994 91
the attraction between NaC
8
and the peptide increases, and hence
some of the water molecules around to the ion are replaced by
peptide molecules. The microscopic region around the ion becomes
bulkier, resulting in a decrease in ionic mobility and consequently
a decrease in K
o
in peptide solutions.
To investigate the behavior of the individual ions comprising
the electrolyte, it is necessary to split into their ionic contributions.
The limiting ionic molar conductance of caprylate anion k
o
(C

8
) va-
lue was calculated by subtracting corresponding value of Na
+
,
k
o
(Na
+
) from K
o
(NaC
8
) values. The k
o
(Na
+
) values in aqueous
dipeptides solutions was taken from our early publication [14].
The calculated values of caprylate anion k
o
(C

8
) are recorded in ta-
ble 5. For a particle of macroscopic dimension moving in a hydro-
dynamic continuum, it is possible to calculate the dimension of the
particle as a function of the ionic molar conductance and viscosity
value of the medium. The hydrodynamic radii of C

8
can be deter-
mined with the Stokes equation [30]
r
st
= Z

F
2
=(6pN
A
k

g); (5)
where Z

is the charge number of the ion, F is the Faraday constant,

N
A
is the Avogadro number, k

is the limiting ionic molar conduc-

tance and g is the viscosity of solvent medium (aqueous peptide
solutions). The values of g and the calculated r
st
values from equa-
tion (5) are included in table 5. For comparison reasons, the crystal-
lographic radii, r
cr
of 0.333 nm for C

8
ion was calculated using the
method provided by Bondi [31]. It can be seen from table 5 that
the Stokes radii are much higher than their crystallographic radii
suggesting that these ions are signicantly solvated in (pep-
tide + water) mixtures.
3.3. Fluorescence spectroscopy
The uorescence probe technique using pyrene as the probe
was used to determine the micelle aggregation behavior of NaC
8
in aqueous glycyl dipeptide solutions. The intensity ratio I
1
/I
3
of
the rst (372 nm) and the third (384 nm) vibronic peaks of the pyr-
ene uorescence spectrum is related to the micropolarity of the
microenvironment in which pyrene is solubilized. Therefore, its
variation shows a change in hydrophobic environment with re-
spect to composition. The I
1
/I
3
of pyrene uorescence as a function
of concentration of NaC
8
in water and in aqueous (0.01, 0.025, and
0.04) mol kg
1
glycyl dipeptide solutions is shown in gure 2. The
2 3 4 5 6 7 8
80
82
84
86
88
V
o
2
.

/
(
c
m
3
m
o
l
-
1
)
n
S
2 3 4 5 6 7 8
4
5
6
7
8
9
10
11
12

t
V
o
/
(
c
m
3
m
o
l
-
1
)
n
S
(a)
(b)
FIGURE 1. The relation of the standard partial molar volume (V

2;/
) in 1.0 mol kg
1
sodium carboxylate solutions (a) and the standard partial molar volumes of transfer
(D
t
V) from water to 1.0 mol kg
1
sodium carboxylate solutions (b) for glycylglycine with the number of carbon atom (n
s
) in the alkyl chains of sodium carboxylate at
T = 298.15 K.
TABLE 4
Values of limiting molar conductivity (K
o
) for sodium caprylate in
water and (water + dipeptide) mixtures at T = 298.15 K.
m
p
/(mol kg
1
) K
o
/(S cm
2
mol
1
)
Water
0.0000 73.79 0.67
73.16
a
(Water + glycylglycine)
0.05000 70.62 0.17
0.1000 68.31 0.21
0.1500 67.43 0.56
0.2000 65.88 0.52
(Water + glycylvaline)
0.05000 70.19 0.20
0.1000 67.99 0.30
0.1500 66.65 0.63
0.2000 63.58 0.21
(Water + glycylleucine)
0.05000 70.06 0.95
0.1000 66.85 0.80
0.1500 63.37 0.18
0.2000 62.97 0.29
a
Reference [29].
TABLE 5
Values of limiting ionic molar conductivity (ko(C

8
)) and Stokes radii (rst (C

8
)) for
caprylate anion in water-dipeptide mixtures at T = 298.15 K.
m
p
/(mol kg
1
) g/(mPa s) k
o
(C

8
)/(S cm
2
mol
1
) r
st
(C

8
)/nm
(Water + glycylglycine)
0.0500 0.910 21.78 0.414
0.1000 0.927 20.42 0.434
0.1500 0.944 20.89 0.416
0.2000 0.960 20.06 0.426
(Water + glycylvaline)
0.0500 0.915 23.93 0.374
0.1000 0.944 22.27 0.390
0.1500 0.972 23.11 0.365
0.2000 1.000 21.29 0.385
(Water + glycylleucine)
0.0500 0.919 22.79 0.392
0.1000 0.952 21.34 0.404
0.1500 0.983 19.55 0.427
0.2000 1.016 20.45 0.395
92 Z. Yan et al. / J. Chem. Thermodynamics 52 (2012) 8994
abrupt sigmoid decrease in I
1
/I
3
clearly indicates that the aggrega-
tion of NaC
8
was formed, and pyrene preferentially resides in a
more hydrophobic microenvironment of the aggregates. These
plots were utilized to estimate the critical micellar concentration,
c
cmc
values of NaC
8
by the sigmoid t. The calculated c
cmc
values
were listed in table 6. The c
cmc
values obtained in water by other
method were also included in table 6. Clearly, those values derived
from laser-Raman spectroscopy [24], conductivity [32,33], and
apparent molar volume [32] are in good agreement with our value.
As can be seen from table 6, the c
cmc
values were found to de-
crease in the presence of dipeptide, the decrease being dependent
upon the concentration of dipeptide. The reason is that the electri-
cal atmosphere in the aqueous surfactant solution altered in the
presence of dipeptide, which neutralizes the effective head group
charge for ionic surfactants resulting in reduced electrostatic
repulsion between the polar head groups and the micelles are
formed at much lower concentration as compared to that in pure
water.
The size of the alkyl chain length of the dipeptides can affect the
c
cmc
of NaC
8
. The marked reduction in c
cmc
in aqueous dipeptide
with longer alkyl chain solutions was observed. This is probably
due to the hydrophobic bonding of longer alkyl chain of glycyl
dipeptides with the exposed hydrocarbon on the micelle surface
and increased hydrophobicity of the micelle. The similar conclu-
0.1 0.2 0.3 0.4 0.5 0.6 0.7
1.1
1.2
1.3
1.4
1.5
1.6
1.7

I
1
/
I
3
c
NaC8
/(mol.dm
-3
)
0.1 0.2 0.3 0.4 0.5 0.6 0.7
1.1
1.2
1.3
1.4
1.5
1.6
1.7

I
1
/

I
3
c
NaC8
/(mol.dm
-3
)
0.1 0.2 0.3 0.4 0.5 0.6 0.7
1.1
1.2
1.3
1.4
1.5
1.6
1.7

I
1
/

I
3
c
NaC8
/(mol.dm
-3
)

(a)
(b)
(c)
FIGURE 2. Variation of the ratio of the rst over the third vibronic band, I
1
/I
3
in the uorescence spectrum of pyrene with NaC
8
concentration (c
NaC8
) in aqueous (a)
glycylglycine, (b) glycylvaline and (c) glycylleucine solutions. Symbol: glycyl dipeptide concentration (mol kg
-1
): 0 (j), 0.01(v), 0.025 (N), 0.04 (.).
TABLE 6
Critical micelle concentration of NaC
8
(c
cmc
) in aqueous solution in presence and absence of dipeptides.
m
p
/(mol kg
-1
) c
cmc
/(mol dm
3
)
Water (Water + glycylglycine) (Water + glycylvaline) (Water + glycylleucine)
0.0000 0.404
0.35
a
, 0.39
b
, 0.40
c
, 0.405
d
0.0100 0.353 0.337 0.304
0.0250 0.313 0.286 0.272
0.0400 0.277 0.266 0.248
a
Reference [24].
b
Reference [32].
c
Reference [32].
d
Reference [33].
Z. Yan et al. / J. Chem. Thermodynamics 52 (2012) 8994 93
sion has been also obtained for ionic surfactant in different size al-
kyl chain glycyl dipeptides, tetraalkylammonium salts and alcohol
solutions [3436].
4. Conclusions
In the present work, the interactions between glycyl dipeptide
and sodium caprylate were studied by volumetric, conductometric
and uorescence methods at T = 298.15 K. The positive V

2;/
and
D
t
V values observed for glycyl dipeptides in the aqueous NaC
8
solution suggest that ionion and ion-polar group interactions
dominate over ionnon-polar and hydrophobichydrophobic
interactions. From the volumetric data, it is suggested that the gly-
cyl dipeptides are solubilized in the palisade layer of sodium cap-
rylate micelles. The decrease in limiting molar conductivities and
the increase in hydrodynamic radii of C

8
in glycyl dipeptide solu-
tions is ascribed to the interaction of NaC
8
with the glycyl dipep-
tides causing the displacement of some of water molecules from
the hydration sphere of ion by peptide molecules. The addition of
glycyl dipeptide in water decreases the c
cmc
values of NaC
8
. The
interaction between NaC
8
and the glycyl dipeptides is dependent
upon their nature and concentration.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China(20973158), Henan Province Excellent Young Foun-
dation (074100510022) and the Science Foundation of Henan
Province (102300410051).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jct.2012.01.024.
References
[1] P.H. Von Hippel, T. Schleich, Structure and Stability of Biological
Macromolecules, vol. 2, Marcel Dekker, New York, 1969.
[2] S.K. Singh, N. Kishore, J. Solution Chem. 32 (2003) 117135.
[3] T.S. Banipal, D. Kuar, P.K. Banipal, J. Chem. Eng. Data 49 (2004) 12361246.
[4] T.S. Banipal, D. Kuar, P.K. Banipal, J. Chem. Thermodyn. 38 (2006) 12141226.
[5] T.S. Banipal, K. Singh, P.K. Banipal, J. Kuar, J. Chem. Thermodyn. 40 (2008)
11661185.
[6] T.S. Banipal, K. Singh, P.K. Banipal, J. Solution Chem. 36 (2007) 16351667.
[7] T.S. Banipal, D. Kaur, P.K. Banipal, G. Singh, J. Mol. Liq. 140 (2008) 5460.
[8] J.J. Wang, Z.N. Yan, J.S. Lu, J. Chem. Thermodyn. 36 (2004) 281288.
[9] J.J. Wang, Z.N. Yan, K.L. Zhuo, J.S. Lu, Biophys. Chem. 80 (1999) 179188.
[10] Z.N. Yan, J.J. Wang, J.S. Lu, J. Chem. Eng. Data 46 (2001) 217222.
[11] J.J. Wang, Z.N. Yan, K.L. Zhuo, D.Z. Liu, Z. Phys. Chem. 214 (2000) 333345.
[12] Z.N. Yan, J.J. Wang, H.L. Zhang, X.P. Xuan, J. Chem. Eng. Data 50 (2005) 1864
1870.
[13] Z.N. Yan, X.G. Wang, Y. Zhao, J.J. Wang, Acta Chim. Sinica 67 (2009) 115121.
[14] Z.N. Yan, Y. Zhao, R.H. Xing, X.G. Wang, J.J. Wang, J. Chem. Eng. Data 55 (2010)
759764.
[15] Z.N. Yan, X.G. Wang, R.H. Xing, J.J. Wang, J. Chem. Eng. Data 54 (2009) 1787
1792.
[16] Z.N. Yan, X.G. Wang, R.H. Xing, J.J. Wang, J. Chem. Thermodyn. 41 (2009) 1343
1349.
[17] Z.N. Yan, W.W. Li, Q. Zhang, X.G. Wang, J.J. Wang, Fluid Phase Equilib. 301
(2011) 156162.
[18] K. Kuwajima, M. Mitani, S. Sugai, J. Mol. Biol. 206 (1989) 547561.
[19] M.J. Schwuger, F.G. Bartnik, Surfactant Sci. Ser. 10 (1980) 149.
[20] W.P. Jencks, Catalysis in Chemistry and Enzymology, McGraw Hill, New York,
1969 (p 351).
[21] H.L. Friedman, C.V. Krishnan, Water: A Comprehensive Treatise, vol. 3, Plenum
Press, New York, 1973 (Chapter 1).
[22] K. Mishra, K.P. Prasad, J.C. Ahluwalia, Biopolymers 22 (1983) 23972409.
[23] K. Rajagopal, S.E. Gladson, J. Chem. Thermodyn. 43 (2011) 852867.
[24] J.B. Rosenholm, P. Stenius, I. Danielsson, J. Colloid Interf. Sci. 57 (1976) 551
563.
[25] E. Vikingstad, J. Colloid Interf. Sci. 72 (1979) 7580.
[26] E. Vikingstad, J. Colloid Interf. Sci. 73 (1980) 500507.
[27] J.J. Wang, Z.N. Yan, Y. Zhao, F.L. Cui, J. Chem. Eng. Data 49 (2004) 13541358.
[28] H.S. Harned, B.B. Owen, The Physical Chemistry of Electrolytic Solutions, Am.
Chem. Soc. Monograph Series, third ed., 1950, p. 155.
[29] N. Campbell, E.M. Kartzmark, G.R. Lakshminarayanan, Can. J. Chem. 40 (1962)
839844.
[30] R.A. Robinson, R. Stokes, Electrolyte Solutions, second ed., Butterworth,
London, 1959.
[31] A. Bondi, J. Phys. Chem. 68 (1964) 441451.
[32] H. Huang, R.E. Verrall, J. Solution Chem. 23 (1994) 925954.
[33] C. Damas, L. Vannier, R. Naejus, R. Coudert, Colloid Surf. A 152 (1999) 183187.
[34] C. Das, B. Das, J. Mol. Liq. 137 (2008) 152158.
[35] M. Benito, A. Garcia, C. Monge, J.M. Saz, M.L. Marina, Colloid Surf. A 125 (1997)
221224.
[36] Z.N. Yan, Q. Zhang, W.W. Li, J.J. Wang, J. Chem. Eng. Data 55 (2010) 35603566.
JCT-11-598
94 Z. Yan et al. / J. Chem. Thermodynamics 52 (2012) 8994