ISSN 00360244, Russian Journal of Physical Chemistry A, 2010, Vol. 84, No. 9, pp. 1598–1604. © Pleiades Publishing, Ltd.

, 2010.
Original Russian Text © B.R. Saifutdinov, V.A. Davankov, M.M. Il’in, S.V. Kurbatova, 2010, published in Zhurnal Fizicheskoi Khimii, 2010, Vol. 84, No. 9, pp. 1750–1756.

PHYSICAL CHEMISTRY
OF SURFACE PHENOMENA

Laws of Sorption of Some Aromatic Heterocycles from Solutions

on Nanoporous Supercrosslinked Polystyrene
B. R. Saifutdinova, V. A. Davankovb, M. M. Il’inb, and S. V. Kurbatovaa
a
Samara State University, Samara, 443048 Russia
b
Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, 117813 Russia
email: sayf_br@mail.ru
Received October 15, 2009

Abstract—Principles of the sorption of 5tetrazole, 1,3,4oxadiazole, and 1,2,4,5tetrazine derivatives from

solutions of various composition on nanoporous supercrosslinked polystyrene were studied by high perfor
mance liquid chromatography. The influence of the nature of heteroatom on the sorption of these heterocy
cles was demonstrated. The role of different types of intermolecular interactions in the sorption of the studied
substances from solutions on nanoporous supercrosslinked polystyrene in quasinormal phase and reverse
phase liquid chromatography are discussed.
DOI: 10.1134/S003602441009027X

INTRODUCTION The purpose of this work was to study principles of

The advantages of supercrosslinked polystyrene
sorbents with respect to those modified by silica and
widely used in high performance liquid chromatogra
phy (HPLC) (e.g., mechanical robustness, chemical
stability, the possibility of using both the quasinormal
phase (QNP) and the reverse phase (RP) modes of
chromatography, and so on) make the application of
these sorbents in the qualitative and quantitative anal
ysis of complex mixtures of substances promising [1,
2]. For these sorbents to be widely used, we obviously
must know the mechanisms for the sorption of mole
cules of various classes of compounds on them. The
results from investigating the sorption and chromato
graphic behavior of substituted benzenes, polycyclic
aromatic compounds, and pyrimidine derivatives on
supercrosslinked polystyrenes were presented in [3–
5]. The high selectivity of aromatic compounds was
noted and it was suggested that, along with dispersion
and orientational (van der Waals) interactions, the
intermolecular interactions (IMI) between π systems
of sorbate molecules and supercrosslinked polystyrene
sorbent (π–π interactions) contribute to the retention
of unsaturated compounds [6, 7]. However, the role of
these interactions in applying the QNP and RP modes
of HPLC to analyze a given sorbent remains insuffi
ciently studied. At the same time, we find the use of the
given compounds as models for investigating the con
tribution from π–π interactions and the formation of
π–d and π–n complexes with the participation of
aromatic fragments of sorbate and sorbent molecules
to a common mechanism of sorption to be quite
promising, due to the possibility of choosing heterocy
cles with different heteroatoms as sorbents.
the sorption of derivatives of several aromatic hetero
cycles from solutions on nanoporous supercrosslinked
polystyrene by means of HPLC.
EXPERIMENTAL
Phenyl, hetaryl, and cyclohexylsubstituted
5terazoles, 1,3,4oxadiazoles, and 1,2,4,5tetrazines
synthesized according to [8], were chosen as sorbates.
The structure of the investigated compounds was con
firmed by IR, 1Н, and 13C NMR spectroscopy.
The experiments were performed on a Tsvet–Yauza
(NPO Khimavtomatika) liquid chromatograph
equipped with a UV spectrophotometric detector. Tet
razole and 1,3,4oxadiazole derivatives were detected
at a wavelength of 254 nm; 1,2,4,5tetrazine deriva
tives, at 280 nm. The sorption behavior of 1,2,4,5tet
razines and 1.3.4oxadiazoles was studied by the RP
(eluent, acetonitrile–water mixture (4 : 1 v/v)) and
QNP (eluent, hexane–methylenedichloride–npro
panol (7 : 2 : 1 v/v)) versions of HPLC. Tetrazole
derivatives were eluted by acetonitrile–water–acetic
acid mobile phase (4 : 1 : 0.1 v/v). Degasation of the
prepared mobile phases was performed by subjecting
them to ultrasound and a helium flow. The expended
volume of eluent was 0.5 ml/min. A chromatographic
column with a length of 150 mm and an internal diam
eter of 4.6 mm, filled with nonmodified hydrophobic
nanoporous supercrosslinked polystyrene sorbent, was
used. The degree of crosslinking was 150%, and the
size of the particles was 3.2 μm. The solutions of sor
bates were prepared by dissolving the individual sub
stances in the corresponding mobile phase; the vol
ume of an injected sample was 10 mcl.

1598
 LAWS OF SORPTION OF SOME AROMATIC HETEROCYCLES
Chromatographic retention of heterocycles was
characterized by the value of the k retention factor [9]
(Tables 1, 2). The volume of mobile phase in the col
umn was equal to the retention volume of sodium
nitrate.
RESULTS AND DISCUSSION
As is well known [10], sorption in liquid chroma
tography is determined by the combination of various
intermolecular interactions (IMI) of sorbate mole
cules with both the solution components and the sur
face of the sorbent. For example, in normal phase
HPLC on polar silicagel, retention is due to the spe
cific interactions with sorbent, and by nonspecific dis
persion and hydrophobic interactions in nonpolar
phases in the RP mode [9, 11]. Since polystyrene is (in
contrast to silica gel) a nonpolar stationary phase, we
refer to quasinormal phase chromatography when it
is combined with nonpolar eluents. Another feature of
the liquid chromatography of compounds containing
multiple bonds on nanoporous supercrosslinking
polystyrenes is the appearance (along with the above
types of IMI) of a contribution from specific sorbate–
sorbent π interactions [7]. In our opinion, the use of
heterocycles with different types of heteroatoms as
sorbates and different eluents in polarity can allow us
to evaluate the ratio of contributions from the above
types of IMI to the common mechanism of sorption
from solutions on nanoporous supercrosslinking poly
styrene.
Table 1 presents the values of the retention factors
for derivatives of 1,2,4,5tetrazine and 1,3,4oxadiaz
ole in the QNP and RP modes of HPLC. As is seen,
the sorption of the studied compounds upon elution
with a hexane–dichlormethane–npropanol mixture
increases in the order cyclohexyl, thienyl, and sele
nophenylsubstituted sorbates. The greater retention
of heterocycles with aromatic substituents as com
pared to the cyclohexylcontaining compounds (sor
bates 9 and 10) is probably due to an additional contri
bution from sorbates 1–8 and 11–19 to retention by
π–πinteractions between the π systems of aromatic
fragments of sorbate molecules and supercrosslinking
polystyrene. 3,6Bis[5di(thienyl2,2')]1,2,4,5tet
razine (sorbate 4) has the maximum value for the
retention factor in QNP HPLC. Among the studied
heterocycles, it contains the highest number of π elec
trons and is consequently more inclined toward π–π
interactions with the sorbent (π stacking) than other
sorbates. The large values of k for thienyl and sele
nophenylsubstituted compounds (as compared to
their phenylsubstituted analogues) are probably also
due to the additional interaction of lone electron pairs
(n electrons) or vacant d orbitals of heteroatoms with
the π systems of crosslinking polystyrene.
In a series of halogensubstituted 1,3,4oxadiaz
oles (sorbates 11–18), the retention factors increase
upon the transition from fluoro to chlorine and bro
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1599
minesubstituted heterocycles. This too is probably
due to interaction between lone electron pairs or
vacant dorbitals of bromine and chlorine atoms and π
systems of supercrosslinking polystyrene. The large
values of k for chlorine (substances 14, 15) and bro
minecontaining (substances 17–19) heterocycles,
while fluorinesubstituted sorbates (substances 11–
13) remain virtually identical to nonsubstituted phe
nyl1,3,4oxadiazoles (substances 5, 6, 8) testify in
favor of the assumption that vacant d orbitals of halo
gen participate in the interaction with sorbent
(Table 1).
The large value of the retention factor of 2(4
nitrophenyl)5(thienyl2)1,3,4oxadiazole (sorbate
19) is apparently due to the participation of the double
bond of the N O nitro group in π–πinteraction
with aromatic fragments of supercrosslinked polysty
rene, and to the possible formation of complexes of
charge transfer between a given sorbate and the π sys
tem of the sorbent due to the semipolar bond of the
heterocycle’s nitro N+ O− group [12].
In the QNP version of the HPLC of 1,2,4,5tetra
zine and 1,3,4oxadiazole derivatives, the ability of
sorbate molecules to participate in specific π–πinter
actions with supercrosslinked polystyrene is a decisive
influence on the retention factor, along with (most
likely) the presence of heteroatoms in analyte mole
cules that contain lone electron pairs or vacant orbitals
capable of participating in the formation of sorbate–
sorbent π–n or π–dcomplexes.
An important step toward understanding the
mechanism of sorption on supercrosslinked polysty
rene in RP HPLC is in our opinion comparing the
retention values of sorbates on this sorbent and the
classical octadecylsilicagel. In [13], we studied the
chromatographic behavior of the same heterocycles
studied in this work under conditions of RP HPLC on
modified C18 silica. It should be noted that the loga
rithms of retention factors for silica correlate well with
the values of the van der Waals volume of molecules
and their lipophilicity. In contrast, such patterns are
not observed in RP HPLC on supercrosslinked poly
styrene. This is probably due to an appreciable contri
bution from specific π interactions with sorbent to the
retention of aromatic heterocycles (in contrast to RP
chromatography on octadecylsilicagel, in which
retention is determined exclusively by the nonspecific
dispersion interactions of substances with the sorbent
and hydrophobic interactions in the eluent [9, 13]).
Cyclohexylsubstituted heterocycles have the
greatest retention in RP HPLC on octadecylsilicagel.
Among the compounds that contain an aromatic sub
stituent, retention declines in the order phenyl–sele
nophenyl–thienyl [13]. The laws of sorption on super
crosslinked polystyrene under conditions of RP are
different from those of chromatography on grafted
Vol. 84 No. 9 2010
1600 SAIFUTDINOV et al.

Table 1. Retention factors of 1,2,4,5tetrazine and 1,3,4oxadiazole derivatives on nanoporous supercrosslinked polysty
rene in both quasinormal phase and reverse phase HPLC

k
No. Compound Structural formula
QNP RP

N N
1 3,6diphenyl1,2,4,5tetrazin 1.27 19.17
N N
N N
2 3,6di(thienyl2)1,2,4,5tetrazine 2.15 17.78
S N N S
N N
3 3,6di(selenophenyl2)1,2,4,5tetrazine 2.59 29.41
Se N N Se
N N
4 3,6bis[5di(thienyl2,2')]1,2,4,5tetrazine 5.86 –
S S N N S S
N N
5 2,5diphenyl1,3,4oxadiazole 0.87 7.80
O
N N
6 2(thienyl2)5phenyl1,3,4oxadiazole 1.11 7.69
S O
N N
7 2,5di(thienyl2)1,3,4oxadiazole 1.29 6.04
S O S
N N
8 2(selenophenyl2)5phenyl1,3,4oxadiazole 1.20 7.96
Se O
N N
9 2phenyl5cyclohexyl1,3,4oxadiazole 0.60 6.34
O
N N
10 2(thienyl2)5cyclohexyl1,3,4oxadiazole 0.67 6.08
S O
N N
11 2phenyl5(4fluorophenyl)1,3,4oxadiazole F 0.88 6.04
O
N N
12 2(thienyl2)5(4fluorophenyl)1,3,4oxadiazole F 1.05 5.85
S O
N N
13 2(selenophenyl2)5(4fluorophenyl)1,3,4oxadiazole F 1.23 6.91
Se O
N N
14 2phenyl5(4chlorophenyl)1,3,4oxadiazole Cl 1.02 10.27
O
N N
15 2(thienyl2)5(4chlorophenyl)1,3,4oxadiazol Cl 1.24 9.94
S O
N N
16 2(4bromophenyl)5phenyl1,3,4oxadiazole Br 1.13 13.41
O
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 9 2010
 LAWS OF SORPTION OF SOME AROMATIC HETEROCYCLES 1601

Table 1. (Contd.)
k
No. Compound Structural formula
QNP RP
N N
17 2(4bromophenyl)5(thienyl2)1,3,4oxadiazole Br 1.39 13.24
S O
N N
18 2(4bromophenyl)5(chlorophenyl2)1,3,4oxadiazole Br 1.57 14.83
Se O
N N
19 2(4nitrophenyl)5(thienyl2)1,3,4oxadiazole NO2 2.41 7.25
S O

Table 2. Retention factors of 5substituted tetrazoles on supercrosslinked polysterene (the eluent was an acetonitrile–wa
ter–acetic acid mixture (4 : 1 : 0.1 v/v))
No. Substance Structural formula k
N N
20 5phenyltetrazole N 0.62
N
H
N N
21 5(thienyl2)tetrazole N 0.71
S N
H
N N
22 5(thienyl3)tetrazole N 0.73
N
S H
N N
23 5(selenophenyl2)tetrazole N 0.85
Se N
H
N N
24 5(4diphenyl)tetrazole N 2.26
N
H
N N
25 5[5di (thienyl2,2')]tetrazole N 2.69
S S N
H
N N
26 5[5di(selenophenyl2,2')]tetrazole N 3.75
Se Se N
H

C18sorbent (Table 1). Selenophenylsubstituted sor
bates (substances 3, 8, 13, 18) thus have the highest
retention factor on supercrosslinked polystyrene.
Slightly lower values of k are typical of phenylsubsti
tuted heterocycles (sorbates 1, 5, 11, 14, 16), while
thienylcontaining compounds (sorbates 2, 6, 7, 12,
15, 17, 19) have intermediate retention factor values.
Cyclohexylsubstituted heterocycles (sorbates 9, 10)
have the lowest k values among the derivatives of
1,3,4oxadiazoles. The low retention of sorbates of
cyclohexylsubstituted sorbates on supercrosslinked
polystyrene is apparently due to the nonplanar struc

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 9 2010

1602 SAIFUTDINOV et al.

k(QNP) bly due to intense hydrophobic interactions in solu

(a) tion), while highly polar 5substituted tetrazoles (due
3
2.6 to the presence of the pyrrole hydrogen atom, which
has acidic properties [14]) are retained only upon elu
2.2 2 tion with mobile phase containing acetic acid, which
suppresses the dissociation of the N–H bond of sor
bate tetrazole fragments [13, 14] (Table 2).
1.8
18 The laws of sorption of the studied heterocycles on
1.4 17 supercrosslinked polystyrene in RP HPLC are thus
7
13 8 15 different from those typical of octadecylsilicagel. This
12 6 apparently indicates the presence of specific sorbate–
1.0 sorbent π interactions whose intensity is comparable
to or greater than the intensity of dispersion interac
4 8 12 16 20 24 28 32
k(RP) tions. In the RP version of HPLC on supercrosslinked
logk(QNP) polystyrene, however, it is necessary to allow for the
0.12 (b) 1 solvation of sorbate molecules by acetonitrile, which
results in less stable sorbate–sorbent π complexes. The
0.08 influence of specific π interactions between molecules
16 of the studied heterocycles and supercrosslinked poly
0.04 styrene on retention is observed in its purest form in
14 the QNP mode of HPLC upon elution with lowpolar
0 mobile phase [7]. In polar solvents in the RP mode, π
interactions function alongside dispersion and hydro
−0.04 phobic and solvation interactions; as a result, their
11 5 total effect on the retention depends on the properties
−0.08 of the chromatographic system as a whole.
The effect of heteroatoms on the sorption of a
0.7 0.8 0.9 1.0 1.1 1.2 1.3
logk(RP) series of 5tetrazole derivatives under RP conditions is
identical to that of the QNP mode of HPLC of
Fig. 1. Correlation between the retention values of
1,2,4,5tetrazine and 1,3,4oxadiazole derivatives
(a) hetaryl and (b) phenylsubstituted 1,2,4,5tetrazines (Table 2). Selenophenylsubstituted tetrazoles are thus
and 1,3,4oxadiazoles in the QNP and RP modes of HPLC. retained on supercrosslinked polystyrene more than
their thienylsubstituted counterparts, which in turn
sorbate more strongly than phenylcontaining sor
ture of this substituent and the lack of conformational bates.
flexibility in the links of the sorbent, in contrast to the
alkyl chains of octadecyl silica [13]. A comparison of the chromatographic behavior of
the studied compounds on C18 sorbent and nanopo
The higher retention of selenophenylsubstituted
rous supercrosslinked polystyrene in RP HPLC shows
sorbates in RP HPLC on supercrosslinked polystyrene
that the retention values on the latter are substantially
(as compared to phenylcontaining heterocycles) is
higher (Tables 1, 2) [13]. This is probably due both to
probably due to the formation of labile complexes with
the greater specific surface of nanoporous super
charge transfer via the participation the π and/or n
crosslinked polystyrene as compared to silica sorbent,
electrons of sorbate and the π system of the sorbent,
and an additional contribution (along with the disper
even upon elution with a polar acetonitrile–water
sion interactions with the sorbent that occur in RP
mobile phase. Under these RP conditions, however, in
HPLC on C18) from specific π–π, π–d, and π–n
contrast to QNP chromatography, fewer thienylsub
stituted sorbates are retained on supercrosslinked interactions between the sorbate and aromatic frag
polystyrene than the corresponding substituted het ments of supercrosslinked polystyrene to the sorption
erocycles. This is apparently a consequence of the of the studied substances.
higher polarity of thienylcontaining compounds rela An analysis of the retention of the studied hetero
tive to phenylcontaining compounds, which leads to cycles leads to the conclusion that no exclusion effects
a higher intensity of the IMI of molecules of these sor are observed during their sorption on the given nanop
bates with a polar water–acetonitrile eluent, and con orous supercrosslinked polystyrene, since the laws of
sequently to their lower retention [13]. their retention correspond to known principles of
It should also be noted that (as in RP HPLC on molecular HPLC [9, 10]. The studied derivatives of
modified silica) nonpolar derivatives of 1,2,4,5tetra 1,3,4oxadiazoles and 1,2,4,5tetrazine, however,
zine have the highest retention of all water–acetoni have volumes close to the van der Waals volume V ~
trile eluents on supercrosslinked polystyrene (proba 640–740 Å3 [13] and similar crosssection sizes.

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A Vol. 84 No. 9 2010

 LAWS OF SORPTION OF SOME AROMATIC HETEROCYCLES
5
12 36
Fig. 2. Separation of a mixture of aromatic heterocycles in RP HPLC on supercrosslinked polystyrene. The mobile phase was an
acetonitrile–water mixture (4:1 v/v).
Along with its obvious analytical applications, the
study of mechanisms of sorption from solutions and
mechanisms of chromatographic retention in HPLC
is of independent heuristic value [15]. Fig. 1 shows the
correlation between the retention factors in QNP and
RP versions of HPLC for hetaryl and phenylsubsti
tuted heterocycles. Such mutual dependences of chro
matographic parameters are usually investigated to
determine the degree of thermodynamical proximity
of the processes in the two systems [9]. The correlation
dependence in the case of supercrosslinked polysty
rene sorbent testifies to the similarity between the
mechanisms of sorption in the QNP and RP modes of
HPLC. This can be interpreted as a manifestation of
specific π interactions with the involvement of sorbent
π systems in both chromatographic systems.
Nevertheless, as follows from Fig. 1, hetaryl(sor
bates 2, 3, 6–8, 12, 13, 15, 17, 18) and phenyl deriva
tives (sorbates 1, 5, 11, 14, 16) of the studied heterocy
cles sorbate by different mechanisms, since the graph
points corresponding to the groups of sorbates linear
ize in different coordinates. This, in our opinion, is an
additional argument in favor of the assumption of a
possible contribution from hetarylsubstituted sor
bates to the retention (with the exception of π–π
interaction) and formation of complexes with charge
transfer involving the participation of lone electron
pairs or the vacant dorbitals of the heteroatom and
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A
1603
14
16
60 84
tR, min
the π systems of nanoporous supercrosslinked polysty
rene.
Fig. 2 shows an example of the chromatographic
separation of some 1,3,4oxadiazoles and 3,6di(thie
nyl2)1,2,4,5tetrazine. As can be seen from the
chromatograms, 3,6di(thienyl2)1,2,4,5tetrazine
(sorbate 2) is retained longer than the others, due
probably to the strong sorption of the heterocycle
owing to the intense hydrophobic interactions
between this nonpolar sorbate and the polar eluent.
CONCLUSIONS
If the pore volume is sterically accessible to the
molecules of sorbates, the presence of centers of sor
bates in the molecules capable of entering into specific
π interactions with aromatic fragments of the sorbent
strongly influences the sorption of aromatic heterocy
cles from solutions on nanoporous supercrosslinked
polystyrene. These are plainly manifested in the non
polar mobile phases of QNP HPLC and largely deter
mine the selectivity of the separations in the polar
mobile phases of RP HPLC. The nature of the solu
tion components, specifically those that interact with
the molecules of heterocycles, also plays a prominent
role
Vol. 84 No. 9 2010
1604 SAIFUTDINOV et al.
ACKNOWLEDGMENTS
The authors are grateful to A. V. Yudashkin, Senior
Researcher at the Samara State University Depart
ment of Organic Chemistry, for kindly donating sam
ples of the compounds studied in work.
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