Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену
Aim. To study the effect of 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]arene and oсtаkis(diethoxyphosphoryloxy)-tert-butylcalix[8]аrene additives to the MeCN – H2O mobile phase (86:14) on the selectivity of the separation of aromatic compounds by the reversed-phase h...
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| Опубліковано в: | Журнал органічної та фармацевтичної хімії |
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| Дата: | 2020 |
| Том: | 18 |
| Випуск: | 3(71) |
| Сторінки: | 43-48 |
| ISSN: | 2518-1548 |
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Репозитарії
Journal of Organic and Pharmaceutical Chemistry| _version_ | 1874455127748771840 |
|---|---|
| author | Kalchenko, Olga I. Vysotsky, Myroslav O. Cherenok, Serhii O. |
| author_facet | Kalchenko, Olga I. Vysotsky, Myroslav O. Cherenok, Serhii O. |
| author_institution_txt_mv | [
{
"author": "Olga I. Kalchenko",
"institution": "Інститут органічної хімії НАН України",
"orcid": ""
},
{
"author": "Myroslav O. Vysotsky",
"institution": "Інститут органічної хімії НАН України",
"orcid": ""
},
{
"author": "Serhii O. Cherenok",
"institution": "Інститут органічної хімії НАН України",
"orcid": ""
}
] |
| author_sort | Kalchenko, Olga I. |
| baseUrl_str | https://ophcj.nuph.edu.ua/oai |
| collection | OJS |
| container_end_page | 48 |
| container_issue | 3(71) |
| container_start_page | 43 |
| container_title | Журнал органічної та фармацевтичної хімії |
| container_volume | 18 |
| datestamp_date | 2026-08-24T17:15:07Z |
| description | Aim. To study the effect of 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]arene and oсtаkis(diethoxyphosphoryloxy)-tert-butylcalix[8]аrene additives to the MeCN – H2O mobile phase (86:14) on the selectivity of the separation of aromatic compounds by the reversed-phase high performance liquid chromatography (RP HPLC) using a Separon SGX C18 support.Results and discussion. The process of complexation of phosphorylated calix[4,8]arenes with benzene derivatives in the mobile phase plays a key role in the RP HPLC separation of analytes. The stability constants of the inclusion complexes and the chromatographic separation coefficients of the analytes depend on the nature of the aromatic compounds and the cavity size of the calixarene macrocycle.Experimental part. The HPLC analysis was performed in acetonitrile – water (86:14) solution using a Separon SGX C18 column. The stability constants of the calixarene complexes were determined using the dependence of 1/k’ chromatographic parameters of benzene derivatives on the calixarene concentration in the mobile phase. Molecular modelling of the calixarene complexes was carried out using a Hyper Chem 8.0 program.Conclusions. The phosphorus-contained calixarenes due to their ability to form supramolecular complexes with aromatic molecules can be used as additives to the RP HPLC mobile phase and improve separation of benzene derivatives.Received: 14.05.2020Revised: 24.06.2020Accepted: 27.08.2020 |
| doi_str_mv | 10.24959/202706 |
| first_indexed | 2025-07-17T13:00:48Z |
| format | Article |
| fulltext |
Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71)
43
ISSN 2518-1548 (Online) ISSN 2308-8303 (Print)
UDC 547.03+547.562 https://doi.org/10.24959/202706
O. I. Kalchenko, M. O. Vysotsky, S. O. Cherenok
Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Ukraine
5, Murmanska str., Kyiv, 02094, Ukraine. E-mail: oik@ioch.kiev.ua
Phosphorylated calix[4,8]arenes improve the RP HPLC
separation of benzene derivatives
Aim. To study the effect of 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]-
arene and oсtаkis(diethoxyphosphoryloxy)-tert-butylcalix[8]аrene additives to the MeCN – H2O mobile phase (86:14)
on the selectivity of the separation of aromatic compounds by the reversed-phase high performance liquid chro-
matography (RP HPLC) using a Separon SGX C18 support.
Results and discussion. The process of complexation of phosphorylated calix[4,8]arenes with benzene
derivatives in the mobile phase plays a key role in the RP HPLC separation of analytes. The stability constants of
the inclusion complexes and the chromatographic separation coefficients of the analytes depend on the nature
of the aromatic compounds and the cavity size of the calixarene macrocycle.
Experimental part. The HPLC analysis was performed in acetonitrile – water (86:14) solution using a Separon
SGX C18 column. The stability constants of the calixarene complexes were determined using the dependence
of 1/k’ chromatographic parameters of benzene derivatives on the calixarene concentration in the mobile phase.
Molecular modelling of the calixarene complexes was carried out using a Hyper Chem 8.0 program.
Conclusions. The phosphorus-contained calixarenes due to their ability to form supramolecular complexes
with aromatic molecules can be used as additives to the RP HPLC mobile phase and improve separation of
benzene derivatives.
Key words: calixarenes; benzene derivatives; inclusion complexes; stability constants; separation
selectivity; RP HPLC; molecular modelling
O. I. Kaльчeнкo, М. О. Висоцький, С. O. Черенок
Інститут органічної хімії НАН України, Україна
Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення
похідних бензену
Мета. Дослідити вплив добавок 5,11,17,23-тетракіс(діізопропоксифосфоніл)-25,26,27,28-тетрапропокси-
калікс[4]арену і октакіс(діетоксифосфорилокси)-трет-бутилкалікс[8]арену до рухомої фази складу MeCN – H2O
(86:14) на селективність розділення ароматичних сполук методом обернено-фазної високоефективної рі-
динної хроматографії (ОФ ВЕРХ) з використанням насадки Separon SGX C18.
Результати та їх обговорення. Процес комплексоутворення фосфорильованих калікс[4,8]aренів з по-
хідними бензену у мобільній фазі відіграє ключову роль у ОФ ВЕРХ розділенні цих аналітів. Константи
стійкості комплексів включення та коефіцієнти хроматографічного розділення аналітів залежать від при-
роди ароматичних сполук та розміру порожнини каліксаренового макроциклу.
Експериментальна частина. ОФ ВЕРХ аналіз проводили у розчині ацетонітрил – вода (86:14) з вико-
ристанням колонки з насадкою Separon SGX C18. Константи стійкості каліксаренових комплексів визначали
із залежності хроматографічних параметрів 1/k’ похідних бензену від концентрації каліксарену в рухомій
фазі. Молекулярне моделювання комплексів каліксаренів виконано за програмою Hyper Chem, версія 8.0.
Висновки. Добавки фосфоровмісних калікс[4,8]аренів до рухомої фази завдяки здатності утворю-
вати комплекси включення з ароматичними молекулами покращують їх ОФ ВЕРХ розділення на насадці
Separon SGX C18.
Ключові слова: каліксарени; похідні бензену; комплекси включення; константи стійкості;
селективність розділення; ОФ ВЕРХ; молекулярне моделювання
Copyright © 2020, O. I. Kalchenko, M. O. Vysotsky, S. O. Cherenok
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0)
Calix[n]arenes – macrocyclic oligomers consisting
of phenolic units linked by methylene spacers are well
known complexаnts that separate different molecu-
les in solutions [1 – 9]. These compounds form supra-
molecular complexes with analyte molecules; they
have been applied for the design of stationary chro-
matographic phases [10 – 16], and as additives to mobi-
le phases [17] that improve the HPLC separation of
organic or inorganic analytes. In this paper we report
the effect of the additives of 5,11,17,23-tetrakis(di-
isopropoxyphosphonyl)-25,26,27,28-tetrapropoxy-
calix[4]arene 1 and oсtаkis(diethoxyphosphoryloxy)-
tert-butylcalix[8]аrene 2 to the acetonitrile – water
mobile phase on the selectivity of the HPLC separa-
tion of some benzene derivatives. The calixarene addi-
tives improve the separation due to the formation of
the host–guest inclusion complexes. The linear charac-
ter of the plots of 1/k’ νs the calixarene concentration
in the mobile phase allows calculating the stability
constants КА of the complexes. The correlations of
the separation selectivity induced by the calixarene
additives with a ratio of the stability constants of
Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71)
44
ISSN 2308-8303 (Print) ISSN 2518-1548 (Online)
the host–guest inclusion complexes of benzene deri-
vatives were found. The complexation is influenced
by logP, the volume and other parameters of analytes
(Fig. 1).
Results and discussion
Complexation of calix[4]arene 1 and calix[8]are-
ne 2 with benzene derivatives was studied by the RP HPLC
method described in papers [18, 19]. Calix[4]аrеne
1 and calix[8]arene 2 were characterized by linear
adsorption isotherms (Fig. 2, 3) that indicated their
reversible adsorption by the column surface. Due to
these characteristics, calix[4,8]arenes 1, 2 are poten-
tial selectors for the RP HPLC separation of analytes.
The calixarene additives to the mobile phase de-
crease the capacity coefficient k’ of benzene deriva-
tives due to the formation of the host–guest inclusion
complexes. The linear plots of 1/k’ νs the calix[4]-
arene and calix[8]arene concentration (Fig. 4, 5) indi-
cate the formation of the host–guest inclusion com-
plexes with stoichiometry in the ratio of 1:1. It allows
using the equation (1) for calculation of their stability
constants КА:
1/k’ = 1/k0’ + KA × [CA]/k0’ ,
whеre: k0’ і k’ are capacity factors of the benzene deriva-
tives determined in the absence and in the presence
of calix[4,8]arenes in the mobile phase.
It has been shown that the addition of calixare-
nes to the mobile phase improves the separation se-
lectivity of benzene analytes (Таbles 1, 2). The sepa-
ration coefficient (α1) calculated as the ratio of the re-
tention times of the pair of analytes depends on the size
of the macrocyclic skeleton, as well as the nature, quan-
tity and position of the substituent in the molecules
of aromatic analytes.
According to the data presented in Table 1, the addi-
tion of phosphorylated calix[4]arene 1 to the mobile
phase increases the analyte separation (α1/α0 = 1.10 – 2.05).
The best separation has been observed for the pairs
of analytes, such as p-aminophenol vs iodobenzene
OPr
OPr
OPr
PrO
P
P
PP
O
O
O
O
O
O
O
O
O
O
O
O
OR
OR
OR
RO
RO
RO
OR
OR
Me
Me
Me
Me Me
Me
Me
MeMe
Me
Me
Me
Me Me
Me
Me
Me Me
Me Me
Me
Me
Me
Me
R:
iPr
P
OEt
OEt
O
iPr
iPr
iPr
iPr
iPr
iPr
iPr
1 2
Fig. 1. Tetrakis(diisopropoxyphosphonyl)tetrapropoxycalix[4]arene 1 and octakis(diethoxyphosphoryloxy)-tert-butylcalix[8]arene 2
0
0.05
0.1
0.15
0.2
0.25
0 20 40 60 80 100 120 140 160
Calixarene concentration,�mol mL
-1
� m
o
l
g
-1
C
a
lix
a
re
n
e
a
d
s
o
rp
ti
o
n
,
.
.
Fig. 2. The adsorption isotherm of tetraphosphorylated
calix[4]arene 1 (R2 = 0.99)
0
2
4
6
8
10
12
14
0 20 40 60 80 100 120 140 160
Calixarene concentration,�mol mL
-1
� m
o
l
g
-1
C
a
lix
a
re
n
e
a
d
s
o
rp
ti
o
n
,
.
.
Fig. 3. The adsorption isotherm of octaphosphorylated
calix[8]arene 2 (R2 = 0.99)
(1)
Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71)
45
ISSN 2518-1548 (Online) ISSN 2308-8303 (Print)
(α1/α0 = 1.78), phenol vs p-aminophenol (α1/α0 = 2.05),
veratrole vs guaiacol (α1/α0 = 1.42), m-toluidine vs
N,N-dimethyl-p-toluidine (α1/α0 = 1.42), and m-xyle-
ne vs chlorobenzene (α1/α0 = 1.36). Other pairs of ana-
lytes were separated by calixarene 1 less effectively.
Calix[8]arene 2 additive to the mobile phase also
improves the separation selectivity of benzene deri-
vatives (α1/α0 = 1.06 – 1.74). The best separation was
observed for the following analytes: resorcinol vs
trichloromethylbenzene (α1/α0 = 1.74), toluene vs
resorcinol (α1/α0 = 1.71), toluene vs p-methylphenol
(α1/α0 = 1.58), trichloromethylbenzene vs trifluoro-
methylbenzene (α1/α0 = 1.49) and phenol vs veratrol
(α1/α0 = 1.32) (Таble 2).
The increase in separation selectivity of the analytes
after the calixarene addition is explained by the forma-
tion of the host–guest inclusion complexes with dif-
ferent adsorption on the stationary phase compa-
red to free analytes. The stability constants КA of
the complexes depend on the calixarene structure,
as well as on the nature, quantity, position of the sub-
stituents in the benzene analytes. The ratio of the se-
paration selectivity (α1/α0), induced by calixarene ad-
ditives 1, 2 correlates with the ratio of the stability
constants of its complexes (S = К1/К2) (Fig. 6, 7).
The complexes can be stabilized by hydrogen bonds,
π–π, С–Н···π, solvophobic interactions and van der Waals
forces between the calixarene and analytes. Fіg. 8 il-
lustrates the energy minimized molecular structures
of calixarene 1 and its complex with р-аmіnophenol.
Calixarene 1 functionalized by phosphonyl groups
at the upper rim of the macrocycle exists in the cone-
conformation (Fіg. 8а). Complexation with p-amino-
phenol does not change the conformation. For calix-
arene 1 there is the possibility of forming two types
of the complexes with p-aminophenol. In the comp-
lex b (Fіg. 8b), the phenolic group forms the hydro-
gen bond with an oxygen atom of the phosphonyl
group at the upper rim. In the complex c (Fіg. 8c),
the phenolic group creates the hydrogen bond with
an ether oxygen atom at the lower rim.
Octaphosphorylated calix[8]arene 2 (Fіg. 9a) that
is larger by size with free rotation of the aromatic frag-
ments around Ar–CH2–Ar bonds changes its confor-
mation after complexation with phenol. A phenol mo-
lecule is located in the center of the calixarene cavi-
ty and forms the hydrogen bond Рh–О–Н···О(Р=O)Ar
with an ether oxygen аtоm (Fіg. 9b).
Еxperimental part
The calixarenes were synthesized by the methods
described previously: 1 [18] and 2 [19]. Acetonitri-
le was obtained from the Acros Organics (Thermo
Fisher Scientific, New Jersey, USА).
HPLC analysis
The HPLC analysis was performed using the liquid
chromatography system (Hitachi, Ltd., Tokyo, Japan).
The column (250 × 4.6 mm i.d.) was packed with Sepa-
ron SGX C18 (Merck, Darmstadt, Germany). Experi-
ments were performed in isocratic conditions. The aceto-
nitrile – water (86:14, v/v) mixture was used as the mo-
bile phase. The calixarene concentrations in the mo-
bile phase were 0.05 – 0.6 mМ. The UV detector was
operated at the wavelength of 254 nm, and the flow
rate was 0.8 mL/min. The samples of the analytes used
for injections were dissolved in the same acetonitrile –
water (86:14, v/v) mixture (c = 0.01 mM). All chro-
matograms were obtained at 26 °C. The mobile phase
which contained the calixarene additive was equili-
brated for 3 h before the analysis. Under these con-
ditions the chromatographic column was saturated
with the calixarene additive.
0
0.05
0.1
0.15
0.2
0.25
0.3
-1 1 3 5 7
[CA], 10-3 M
1
/k
'
veratrol guaiacol phenol
benzene toluene trifluorometh
.
Fig. 4. Plots of 1/k’ for some benzene derivatives:
veratrol, guaiacol, phenol, benzene, toluene
and trichloromethylbenzene νs the calix[4]arene 1
concentration in the mobile phase
(R2 = 0.95 – 0.99)
0.1
0.14
0.18
0.22
0.26
0.3
-1 1 3 5 7
1
/k
'
p-bromophenol p-fluorophenol chlorobenzene
p-chlorophenol trichlorometh m-xylene
p-aminophenol
[CA], 10-4 M.
Fig. 5. Plots of 1/k’ for some benzene derivatives: p-bromophenol,
p-fluorophenol, chlorobenzene, p-chlorophenol,
trichloromethylbenzene, m-xylene and p-aminophenol νs
the calix[8]arene 2 concentration in the mobile phase
(R2 = 0.95 – 0.99)
Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71)
46
ISSN 2308-8303 (Print) ISSN 2518-1548 (Online)
Таble 1
The separation selectivity* of the benzene derivatives induced by calіx[4]arene 1 additive
Analytes separated
Selectivity
without
calixarene 1
additive, α0
Selectivity
with
calixarene 1
additive, α1
Selectivity
ratio, α1/α0
Stability
constant ratio,
S = K1/K2 [18]
veratrol vs guaiacol 1.18 1.67 1.42 2.02
p-xylene vs isopropylbenzene 2.00 2.20 1.10 1.11
guaiacol vs trifluoromethylbenzene 1.78 1.88 1.10 1.09
p-xylene vs benzyl alcohol 1.82 1.98 1.10 1.39
p-cyanophenol vs p-aminophenol 1.20 1.44 1.20 1.06
m-xylene vs chlorobenzene 1.00 1.36 1.36 2.58
p-fluorophenol vs trifluoromethylbenzene 1.00 1.11 1.11 1.03
m-toluidine vs N,N-dimethyl-p-toluidine 3.65 5.20 1.42 1.88
toluene vs p-methoxytoluene 3.31 4.50 1.36 1.81
phenol vs guaiacol 1.03 1.77 1.71 4.06
p-aminophenol vs iodobenzene 1.53 2.72 1.78 4.70
phenol vs m-nitropenol 1.68 1.86 1.11 1.22
phenol vs p-aminophenol 1.11 2.28 2.05 10.28
trifluoromethylbenzene vs trichloromethylbenzene 2.28 3.47 1.52 10.92
Notes: * – the uncertainties of the parameters were 5 – 7 %.
Таble 2
The separation selectivity* of the benzene derivatives induced by calіx[8]arene 2 additive
Analytes separated
Selectivity without
calixarene 2
additive, α0
Selectivity with
calixarene 2
additive, α1
Selectivity
ratio, α1/α0
Stability
constant ratio,
S = K1/K2 [19]
benzene vs phenol 1.11 1.47 1.22 1.40
phenol vs p-chlorophenol 1.04 1.17 1.13 1.12
phenol vs p-methylphenol 1.04 1.06 1.02 1.18
phenol vs guaiacol 1.03 1.09 1.06 1.18
phenol vs resorcinol 1.08 1.15 1.06 1.32
phenol vs veratrol 1.00 1.32 1.32 1.25
toluene vs resorcinol 1.12 1.91 1.71 1.22
benzene vs trichloromethylbenzene 2.55 3.41 1.34 2.43
benzene vs toluene 1.04 1.36 1.31 1.55
benzene vs resorcinol 1.08 1.40 1.30 1.89
benzene vs trifluoromethylbenzene 1.77 1.97 1.11 1.22
trichloromethylbenzene vs trifluoromethylbenzene 1.29 1.92 1.49 2.96
benzene vs guaiacol 1.02 1.12 1.10 1.18
benzene vs veratrole 1.00 1.06 1.06 1.12
toluene vs p-methylphenol 1.00 1.58 1.58 1.07
resorcinol vs p-fluorophenol 1.03 1.43 1.38 2.02
resorcinol vs p-chlorophenol 1.12 1.34 1.20 1.21
resorcinol vs trifluoromethylbenzene 2.13 2.49 1.17 1.55
resorcinol vs trichloromethylbenzene 2.75 4.79 1.74 4.59
Notes: * – the uncertainties of the parameters were 5 – 7 %
Журнал органічної та фармацевтичної хімії. – 2020. – Т. 18, вип. 3 (71)
47
ISSN 2518-1548 (Online) ISSN 2308-8303 (Print)
Molecular modelling
The molecular modelling of calixarenes 1, 2 and
their complexes with the analytes was carried out by
the molecular mechanics ММ+method, the force field
(PM3) (Hyper Chem software package, version 8) [20].
The structures were calculated by the semi-empiri-
cal method. The RMS (standard deviation of the word
root mean square) gradient was equal to 0.01 kcal/A·mol.
Conclusions
The addition of phosphorylated derivatives of
calix[4]arene and calix[8]arene to the acetonitrile –
water mobile phase improves the selectivity of the chro-
matographic separation of benzene analytes on the Sepa-
ron SGX C18 stationary phase under HPLC. The im-
provement of the separation selectivity is explained
by forming calixarene – analyte inclusion complexes
with different sorption on the stationary phase com-
pared to those of free analytes. The efficacy of such
separation depends on the size of the calixarene
backbone, as well as the nature, number and posi-
tion of the substituents in the benzene analyte de-
termining the structure and stability of the inclusion
complexes.
Conflict of interests: authors have no conflict of
interests to declare.
0.8
1
1.2
1.4
1.6
1.8
2
2.2
0.8 1.3 1.8 2.3 2.8 3.3 3.8 4.3 4.8 5.3
K1/K2
� 1
/ �
2
Fig. 6. Plots of the ratio of selectivity separation (α1/α0)
of the analytes vs the ratio of the stability constants
(S = К1/К2
) of their host–guest complexes
with calix[4]arene 1 (R2 = 0.94)
0.8
1
1.2
1.4
1.6
1.8
2
0.8 1.3 1.8 2.3 2.8 3.3 3.8 4.3 4.8
K1/K2
� 1
/ �
2
Fig. 7. Plots of the ratio of selectivity separation (α1/α0)
of the analytes vs the ratio of the stability constants
(S = К1/К2
) of their host–guest complexes
with calix[8]arene 2 (R2 = 0.87)
Fіg. 8. The energy minimized molecular structures of calixarene 1 (a) and its complexes with р-аmіnоphеnоl stabilized by the hydrogen
bonds Ar–О–Н…O=P at the upper rim (b) and Ar–О–Н…О(Рr) at the lower rim (c) of the macrocycle
Fіg. 9. The energy minimized molecular structure of calix[8]arene 2 (а) and its phenol complex (b)
Journal of Organic and Pharmaceutical Chemistry. – 2020. – Vol. 18, Iss. 3 (71)
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ISSN 2308-8303 (Print) ISSN 2518-1548 (Online)
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Received: 14. 05. 2020
Revised: 24. 06. 2020
Accepted: 27. 08. 2020
The work was supported by the National Academy of Sciences of Ukraine through the project “Functionalized calixarenes for recognition,
binding and transport of biomolecules” (the state registration: No. 0108U003174).
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| id | oai:ojs.journals.uran.ua:article-202706 |
| institution | Journal of Organic and Pharmaceutical Chemistry |
| issn | 2518-1548 |
| keywords_txt_mv | |
| language | English |
| last_indexed | 2026-08-25T01:01:52Z |
| publishDate | 2020 |
| publisher | National University of Pharmacy |
| record_format | ojs |
| resource_txt_mv | ophcjnupheduua/97/a668c5fcd540b28be837ffbaa4f92797.pdf |
| spelling | oai:ojs.journals.uran.ua:article-2027062026-08-24T17:15:07Z Phosphorylated calix[4,8]arenes improve the RP HPLC separation of benzene derivatives Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену Kalchenko, Olga I. Vysotsky, Myroslav O. Cherenok, Serhii O. calixarenes benzene derivatives inclusion complexes stability constants separation selectivity RP HPLC molecular modelling 547.03 547.562 каліксарени похідні бензену комплекси включення константи стійкості селективність розділення ОФ ВЕРХ молекулярне моделювання 547.03 547.562 Aim. To study the effect of 5,11,17,23-tetrakis(diisopropoxyphosphonyl)-25,26,27,28-tetrapropoxycalix[4]arene and oсtаkis(diethoxyphosphoryloxy)-tert-butylcalix[8]аrene additives to the MeCN – H2O mobile phase (86:14) on the selectivity of the separation of aromatic compounds by the reversed-phase high performance liquid chromatography (RP HPLC) using a Separon SGX C18 support.Results and discussion. The process of complexation of phosphorylated calix[4,8]arenes with benzene derivatives in the mobile phase plays a key role in the RP HPLC separation of analytes. The stability constants of the inclusion complexes and the chromatographic separation coefficients of the analytes depend on the nature of the aromatic compounds and the cavity size of the calixarene macrocycle.Experimental part. The HPLC analysis was performed in acetonitrile – water (86:14) solution using a Separon SGX C18 column. The stability constants of the calixarene complexes were determined using the dependence of 1/k’ chromatographic parameters of benzene derivatives on the calixarene concentration in the mobile phase. Molecular modelling of the calixarene complexes was carried out using a Hyper Chem 8.0 program.Conclusions. The phosphorus-contained calixarenes due to their ability to form supramolecular complexes with aromatic molecules can be used as additives to the RP HPLC mobile phase and improve separation of benzene derivatives.Received: 14.05.2020Revised: 24.06.2020Accepted: 27.08.2020 Мета. Дослідити вплив добавок 5,11,17,23-тетракіс(діізопропоксифосфоніл)-25,26,27,28-тетрапропоксикалікс[4]арену і октакіс(діетоксифосфорилокси)-трет-бутилкалікс[8]арену до рухомої фази складу MeCN – H2O (86:14) на селективність розділення ароматичних сполук методом обернено-фазної високоефективної рідинної хроматографії (ОФ ВЕРХ) з використанням насадки Separon SGX C18.Результати та їх обговорення. Процес комплексоутворення фосфорильованих калікс[4,8]aренів з похідними бензену у мобільній фазі відіграє ключову роль у ОФ ВЕРХ розділенні цих аналітів. Константи стійкості комплексів включення та коефіцієнти хроматографічного розділення аналітів залежать від природи ароматичних сполук та розміру порожнини каліксаренового макроциклу.Експериментальна частина. ОФ ВЕРХ аналіз проводили у розчині ацетонітрил – вода (86:14) з використанням колонки з насадкою Separon SGX C18. Константи стійкості каліксаренових комплексів визначали із залежності хроматографічних параметрів 1/k’ похідних бензену від концентрації каліксарену в рухомій фазі. Молекулярне моделювання комплексів каліксаренів виконано за програмою Hyper Chem, версія 8.0.Висновки. Добавки фосфоровмісних калікс[4,8]аренів до рухомої фази завдяки здатності утворювати комплекси включення з ароматичними молекулами покращують їх ОФ ВЕРХ розділення на насадці Separon SGX C18.Received: 14.05.2020 Revised: 24.06.2020 Accepted: 27.08.2020 National University of Pharmacy 2020-09-18 Article Article application/pdf https://ophcj.nuph.edu.ua/article/view/ophcj.20.202706 10.24959/202706 Journal of Organic and Pharmaceutical Chemistry; Vol. 18 No. 3(71) (2020); 43-48 Журнал органической и фармацевтической химии; Том 18 № 3(71) (2020); 43-48 Журнал органічної та фармацевтичної хімії; Том 18 № 3(71) (2020); 43-48 2518-1548 2308-8303 en https://ophcj.nuph.edu.ua/article/view/ophcj.20.202706/213158 Copyright (c) 2020 Olga I. Kalchenko, Myroslav O. Vysotsky, Serhii O. Cherenok https://creativecommons.org/licenses/by/4.0 |
| spellingShingle | каліксарени похідні бензену комплекси включення константи стійкості селективність розділення ОФ ВЕРХ молекулярне моделювання 547.03 547.562 Kalchenko, Olga I. Vysotsky, Myroslav O. Cherenok, Serhii O. Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title | Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title_alt | Phosphorylated calix[4,8]arenes improve the RP HPLC separation of benzene derivatives |
| title_full | Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title_fullStr | Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title_full_unstemmed | Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title_short | Фосфорильовані калікс[4,8]aрени покращують ОФ ВЕРХ розділення похідних бензену |
| title_sort | фосфорильовані калікс[4,8]aрени покращують оф верх розділення похідних бензену |
| topic | каліксарени похідні бензену комплекси включення константи стійкості селективність розділення ОФ ВЕРХ молекулярне моделювання 547.03 547.562 |
| topic_facet | calixarenes benzene derivatives inclusion complexes stability constants separation selectivity RP HPLC molecular modelling 547.03 547.562 каліксарени похідні бензену комплекси включення константи стійкості селективність розділення ОФ ВЕРХ молекулярне моделювання 547.03 547.562 |
| url | https://ophcj.nuph.edu.ua/article/view/ophcj.20.202706 |
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