Sorption and enantioselective properties of binary stationary phases based on polydimethylsiloxane and polyethyleneglycol and additive of heptakis-(2,3-Odiacetyl- 6-O-tosyl)-β-cyclodextrin under gas chromatography conditions
Abstract
The subject of the study were two binary polymer systems – non-polar (polydimethylsiloxane PMS,
Mr=5000) and polar (polyethyleneglycol, PEG, Mr=400) with the addition of (10 wt.%) of first synthesized
bifunctional derivative of β-cyclodextrin – heptakis-(2,3-O-diacetyl-6-O-tosyl)-β-cyclodextrin (Ac-Tz-β-
CD). The aim of the work was to study the thermodynamic characteristics of sorption and complexation of
the type of "guest - host" for volatile organic compounds in the columns with binary stationary phases based
on polymers (PMS, PEG) and chiral additive (Ac-Tz- β-CD).
Method of inverse gas chromatography was used to determine the specific retention volumes for 29
organic compounds of different classes, including optically active; for columns with binary fixed source
"pure" polymers enthalpy and entropy contributions to the retention and thermodynamic characteristics of
complex formation were calculated.
It was established that in the system "PMS - Ac-Tz-β-CD" complexation of the "guest - host" type is
weak, with the exception of polar compounds with a small molecular volume. This phase has a high
enantioselectivity in relation to the optical isomers of menthol in a wide temperature range. For a large number of investigated non-polar and polar sorbates in the system "PEG - Ac-Tz-β-CD" complexation with
exothermic heat effect was observed. This system has a moderate enantioselectivity towards terpene
hydrocarbons.
The results of the work are important for the development of supramolecular chemistry of polymeric
systems, and the development and manufacture of capillary separation columns of type WCOT for chiral gas
chromatography. For the first time a bifunctional derivative β-cyclodextrin - heptakis-(2,3-O-diacetyl-6-Otosyl)-
β-cyclodextrin was used as a component of mixed polymeric sorbent for gas-liquid chromatography. It
is shown that the nature of the sorbent polymer matrix affects the ability of complexing with dissolved
organic compounds Ac-Tz-β-CD. With use of polyethyleneglycol - 400 complexing effect was observed for
more organic compounds than with polydimethylsiloxane. Polydimethylsiloxane-based sorbent showed
higher enantioselective properties relative to the isomers of menthol, while the sorbent on the
polyethyleneglycol basis showed enantioselective properties with respect to the optical isomers of limonene
and camphene
Downloads
References
chromatography, Trends in analytical chemistry,
2002, V. 21, No 9+10, pp. 647-661.
2. Schurig V. Separation of enantiomers by
gas chromatography. J. of Chromatography A,
2001, V. 906, pp. 275-299.
3. Schurig V. Practice and theory of
enantioselective complexation gas
chromatography, J. of Chromatography A, 2002,
V. 965, pp. 315-356.
4. Juvancz Z. The role of cyclodextrins in
chiral selective chromatography, Trends in analytical chemistry, 2002, V. 21, No 5,
pp. 379-388.
5. Shitangkoona A., Yanchindaa J.,
Shiowatana J. Thermodynamic study on the gas
chromatographic separation of the enantiomers
of aromatic alcohols using heptakis(2,3-di-Omethyl-
6-O-tret-butyldimethylsilyl)-β-cyclodextrin
as a stationary phase, J. Chromatogr. A,
2004, V. 1049, pp. 223-226.
6. Suhua Qi, Ping Ai, Cenyi Wang et al. The
characteristics of a mixed stationary phase
containing Permethylated-b-CD and Perpentylated-
b-CD in gas chromatography, Separation
and Purification Technology, 2006, V. 48, pp.
310-313.
7. Tisse S., Peulon-Agasse V., Cardina P.,
Bouillon J.-P., Combret J.-C.. Capillary gas
chromatographic properties of three new monoesterpermethylated
β-cyclodextrin derivatives,
Anal. chim. Acta, 2006, V. 560, pp. 207-217.
8. Takahisa E., Engel K.-H. 2,3-Di-Omethoxymethyl-
6-O-tert-butyldimethylsilyl-γ-
cyclodextrin: a new class of cyclodextrin
derivatives for gas chromatographic separation
of enantiomers. J. Chromatogr. A, 2005, vol.
1063, pp.181-192.
9. Belyakov L.A., Varvarin A.M., Khora A.V.
Adsorbtsionnaya i khimicheskaya immobilizatsiya
β-tsiklodekstrina na poverkhnosti
dispersionnykh kremnezemov [Adsorption and
chemical immobilization of β-cyclodextrin on
the surface of silica dispersion], Ukrainskii
khimicheskii zhurnal, 2006, V. 72, No 3, pp. 30-
35.
10. Kartsova L.A., Makarov A.A., Popova
A.M. Quantitative evaluation of interactions of
organic compounds with 18-crown ethers and β-
cyclodextrin as components of stationary phases
for gas chromatography, J. analyt. chemistry,
2007, V. 62, No 3, pp. 270-276.
11. Grisales J.O., Lebed P.J., Keunchkarian S.
et al. Permethylated β-cyclodextrin in liquid
poly(oxyethylene) as a stationary phase for
capillary gas chromatography, J. Chromatogr. A,
2009, V. 1216, pp. 6844-6851.
12. Asztemborska M., Bielejewska A.,
Duszczyk K. et al. Comparative study on
camphor enantiomers behavior under the
conditions of gas-liquid chromatography and
reversed-phase high-performance liquid
chromatography systems modified with a- and
b-cyclodextrins, J. Chromatogr. A, 2000, V.
874, pp. 73-80.
13. Asztemborska M., Nowakowski R.,
Sybilska D. Separation ability and stoichiometry
of cyclodextrin complexes, J. Chromatogr. A,
2000, V. 902, pp. 381-387.
14. Asztemborska M., Sybilska D.,
Nowakowski R., Perez G. Chiral recognition
ability of α-cyclodextrin with regard to some
monoterpenoids under gas–liquid
chromatographic conditions, J. Chromatogr A,
2003, V. 1010, pp. 233-242.
15. Skorka M., Asztemborska M., Zukowski J.
Thermodynamic studies of complexation and
enantiorecognition processes of monoterpenoids
by α- and β-cyclodextrin in gas chromatography,
J. Chromatogr. A, 2005, V. 1078, pp.136-143.
16. Platonov V.I., Kuraeva Yu.G., Kazurov
D.M. et al. Sorbtsionnye svoistva smeshannoi
statsionarnoi fazy «polidimetilsiloksan -
permetilirovannnyi β-tsiklodekstrin» v usloviyakh
gazovoi khromatografii (Sorption
properties of mixed stationary phase
«polydimethylsiloxane - permethylated β-
cyclodextrin» in a gas chromatography), Vestnik
SamGU, 2012, No 3/1 (94), pp. 164-172.
17. Onuchak L.A., Platonov V.I., Kuraeva
Yu.G. Thermodynamics of the adsorption of
volatile organic compounds in a binary
polydimethylsiloxane-permethylated β-
cyclodextrin stationary phase, as measured by
gas chromatography, Russian journal of physical
chemistry A, 2013, V. 87, No 5, pp. 861-864.
18. Onuchak L.A., Kuraeva Yu.G., Platonov
V.I., Chvanov V.O. Gazokhromatograficheskoe
issledovanie sorbtsionnykh svoistv smeshannoi
polimernoi fazy, soderzhashchei atsetilirovannyi
β-tsiklodekstrin [Gas chromatographic study of
the sorption properties of the polymer mixed
phase comprising an acetylated β-cyclodextrin],
Sorbtsionnye i khromatograficheskie protsessy,
2012, V. 12, No 3, pp. 345-354.
19. Zhdanov Yu.A., Dorofeenko G.N.,
Korol'chenko G.A., Bogdanova G.V. Praktikum
po khimii uglevodovov, M.: Rosvuzizdat, 1963,
120 p.
20. Yashin Ya.I., Yashin E.Ya., Yashin A.Ya.
Gazovaya khromatografiya, M.: Izdatel'stvo
«TransLit», 2009, 528 p.
21. Kolb B. Gazovaya khromatografiya s
primerami i illyustratsiyami – Samara: Izdatel'stvo
«Samarskii universitet», 2007, 243 p.
21. Stid Dzh.V., Etvud Dzh. L.
Supramolekulyarnaya khimiya. M.: IKTs
«Akademkniga», 2007, 480 p.
