122 research outputs found
ΠΠ ΠΠΠΠΠΠΠΠ ΠΠΠ‘ΠΠΠ Π‘ΠΠΠΠΠΠ ΠΠΠΠΠΠ‘Π’ΠΠ-ΠΠΠΠΠΠ‘Π’ΠΠΠ ΠΠΠΠ ΠΠΠΠ‘Π’Π ΠΠΠ¦ΠΠ Π‘ ΠΠ‘ΠΠΠΠ¬ΠΠΠΠΠΠΠΠ Π ΠΠΠ§ΠΠ‘Π’ΠΠ ΠΠΠ‘Π’Π ΠΠΠΠΠ’Π 3-ΠΠΠ’ΠΠ-1-ΠΠΠ’ΠΠ-ΠΠΠΠΠΠΠΠΠΠ Π’ΠΠ’Π ΠΠ€Π’ΠΠ ΠΠΠ ΠΠ’Π ΠΠΠ― ΠΠΠΠΠ’Π ΠΠ€ΠΠ ΠΠ’ΠΠ§ΠΠ‘ΠΠΠΠ ΠΠΠ ΠΠΠΠΠΠΠΠ― Π‘Π’ΠΠ ΠΠΠΠΠ«Π₯ ΠΠΠ ΠΠΠΠΠ Π ΠΠΠ ΠΠΠ¦ΠΠ₯ ΠΠΠ§Π
In the current research, a method of electrophoretic determination of steroid hormones in urine sample with the use of dispersive liquid-liquid microextraction in imidazolium ionic liquid C8MImBF4 during thesample preparation step was proposed. Ionic liquids Π‘6MImNTf2, Π‘6MImBF4, Π‘8MImBF4 were examined as extractants while acetone, methanol and acetonitrile were tested as dispersants. Β It was found that the IL nature influences the extraction of steroid hormones, i.e.Β the extraction degrees were raised when IL with BF4- anion was used instead of NTf2,and when the length of alkyl radical in imidazolium cation was increased. It was also established that pH of water phase did not affect the steroid hormones extraction. The highest extraction degree values of analytes (69-93%) were obtained under the following condition: addition of 150 mkl of IL C8MImBF4 dissolved in 0.5 ml of acetone to 5 ml aqueous sample. The developed sample preparation technique was successfully applied to the determination of corticosteroid in urine. It was found that the high concentration of salt in the sample matrix favors the mass transfer of analyte to organic phase, and the extraction degrees in IL were increased. The preconcentration factors in sample preparation were 23-30; the achieved limits of quantification were 8-12 ng/ml.Β Β Β Β Β Β Β Β Keywords: imidazolium ionic liquids, liquid-liquid microextraction, dispersive liquid-liquid microextraction, steroid hormones, capillary electrophoresisDOI: http://dx.doi.org/10.15826/analitika.2018.22.3.011(Russian)E.A. Kolobova1, L.A. Kartsova2Β 1TheΒ Nikiforov Russian CenterΒ of Emergency and Radiation Medicine, 54 Optikov st.,St. Petersburg, 199034, Russian Federation2Saint-Petersburg State University, Institute of Chemistry, 26 Universitetskii prospect,Β St. Petersburg, Petergof 198504, Russian FederationΠ ΡΠ°Π±ΠΎΡΠ΅ ΠΏΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ Π²Π°ΡΠΈΠ°Π½ΡΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ² Π² ΠΎΠ±ΡΠ°Π·ΡΠ°Ρ
ΠΌΠΎΡΠΈ Ρ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Π½Π° ΡΡΠ°Π΄ΠΈΠΈ ΠΏΡΠΎΠ±ΠΎΠΏΠΎΠ΄Π³ΠΎΡΠΎΠ²ΠΊΠΈ Π΄ΠΈΡΠΏΠ΅ΡΡΠΈΠΎΠ½Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎ-ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎΠΉ ΠΌΠΈΠΊΡΠΎΡΠΊΡΡΡΠ°ΠΊΡΠΈΠΈ Π² ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»ΠΈΠ΅Π²ΡΡ ΠΈΠΎΠ½Π½ΡΡ ΠΆΠΈΠ΄ΠΊΠΎΡΡΡ (ΠΠ). Π ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΡΠΊΡΡΡΠ°Π³Π΅Π½ΡΠ° Π±ΡΠ»ΠΈ Π°ΠΏΡΠΎΠ±ΠΈΡΠΎΠ²Π°Π½Ρ ΠΠ Π‘6MImNTf2, Π‘6MImBF4, Π‘8MImBF4, Π° Π² ΡΠΎΠ»ΠΈ Π΄ΠΈΡΠΏΠ΅ΡΠ³Π°ΡΠΎΡΠ° ΠΈΡΠΏΡΡΠ°Π½Ρ ΠΌΠ΅ΡΠ°Π½ΠΎΠ», Π°ΡΠ΅ΡΠΎΠ½ΠΈΡΡΠΈΠ», Π°ΡΠ΅ΡΠΎΠ½. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΠΏΡΠΈΡΠΎΠ΄Π° ΠΠ Π²Π»ΠΈΡΠ΅Ρ Π½Π° ΠΏΠΎΠ»Π½ΠΎΡΡ ΡΠΊΡΡΡΠ°ΠΊΡΠΈΠΈ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ²: ΡΡΠ΅ΠΏΠ΅Π½ΠΈ ΠΈΠ·Π²Π»Π΅ΡΠ΅Π½ΠΈΡ Π°Π½Π°Π»ΠΈΡΠΎΠ² Π²ΠΎΠ·ΡΠ°ΡΡΠ°ΡΡ ΠΏΡΠΈ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠΈ ΠΠ Ρ Π°Π½ΠΈΠΎΠ½ΠΎΠΌ BF4- Π²ΠΌΠ΅ΡΡΠΎ NTf2- ΠΈ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΠΈ Π΄Π»ΠΈΠ½Ρ Π°Π»ΠΊΠΈΠ»ΡΠ½ΠΎΠ³ΠΎ ΡΠ°Π΄ΠΈΠΊΠ°Π»Π° Π² ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»ΠΈΠ΅Π²ΠΎΠΌ ΠΊΠ°ΡΠΈΠΎΠ½Π΅. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ ΡΠ Π²ΠΎΠ΄Π½ΠΎΠΉ ΡΠ°Π·Ρ Π½Π΅ Π²Π»ΠΈΡΠ΅Ρ Π½Π° ΡΠΊΡΡΡΠ°ΠΊΡΠΈΡ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ². ΠΠ°ΠΈΠ±ΠΎΠ»ΡΡΠΈΠ΅ Π·Π½Π°ΡΠ΅Π½ΠΈΡ ΡΡΠ΅ΠΏΠ΅Π½Π΅ΠΉ ΠΈΠ·Π²Π»Π΅ΡΠ΅Π½ΠΈΡ Π°Π½Π°Π»ΠΈΡΠΎΠ² (69-93 %) ΠΏΠΎΠ»ΡΡΠ΅Π½Ρ ΠΏΡΠΈ Π΄ΠΎΠ±Π°Π²Π»Π΅Π½ΠΈΠΈ ΠΊ 5 ΠΌΠ» Π²ΠΎΠ΄Π½ΠΎΠ³ΠΎ ΠΎΠ±ΡΠ°Π·ΡΠ° 150 ΠΌΠΊΠ» ΠΈΠΎΠ½Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠΈ C8MImBF4, ΡΠ°ΡΡΠ²ΠΎΡΠ΅Π½Π½ΠΎΠΉ Π² 0.5 ΠΌΠ» Π°ΡΠ΅ΡΠΎΠ½Π°. Π Π°Π·ΡΠ°Π±ΠΎΡΠ°Π½Π½ΡΠΉ Π²Π°ΡΠΈΠ°Π½Ρ ΠΏΡΠΎΠ±ΠΎΠΏΠΎΠ΄Π³ΠΎΡΠΎΠ²ΠΊΠΈ Π±ΡΠ» ΡΡΠΏΠ΅ΡΠ½ΠΎ ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ ΠΏΡΠΈ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠ΅ ΠΊΠΎΡΡΠΈΠΊΠΎΡΡΠ΅ΡΠΎΠΈΠ΄ΠΎΠ² Π² ΠΎΠ±ΡΠ°Π·ΡΠ°Ρ
ΠΌΠΎΡΠΈ. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π²ΡΡΠΎΠΊΠ°Ρ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΡ ΡΠΎΠ»Π΅Π²ΡΡ
ΠΊΠΎΠΌΠΏΠΎΠ½Π΅Π½ΡΠΎΠ² Π² ΠΌΠ°ΡΡΠΈΡΠ΅ ΠΏΡΠΎΠ±Ρ Π±Π»Π°Π³ΠΎΠΏΡΠΈΡΡΡΡΠ²ΡΡΡ ΠΌΠ°ΡΡΠΎΠΏΠ΅ΡΠ΅Π½ΠΎΡΡ Π°Π½Π°Π»ΠΈΡΠΎΠ² Π² ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΡΡ ΡΠ°Π·Ρ ΠΈ ΡΡΠ΅ΠΏΠ΅Π½ΠΈ ΠΈΠ·Π²Π»Π΅ΡΠ΅Π½ΠΈΡ Π² ΠΠ ΡΠ²Π΅Π»ΠΈΡΠΈΠ²Π°ΡΡΡΡ. Π€Π°ΠΊΡΠΎΡΡ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ Π² ΠΏΡΠΎΡΠ΅ΡΡΠ΅ ΠΏΡΠΎΠ±ΠΎΠΏΠΎΠ΄Π³ΠΎΡΠΎΠ²ΠΊΠΈ ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ 23-30; Π΄ΠΎΡΡΠΈΠ³Π½ΡΡΡΠ΅ ΠΏΡΠ΅Π΄Π΅Π»Ρ ΠΊΠΎΠ»ΠΈΡΠ΅ΡΡΠ²Π΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡΒ - 8-12 Π½Π³/ΠΌΠ».Β Β Β Β Β Β Β Β ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»ΠΈΠ΅Π²ΡΠ΅ ΠΈΠΎΠ½Π½ΡΠ΅ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠΈ, ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎ-ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½Π°Ρ ΡΠΊΡΡΡΠ°ΠΊΡΠΈΡ, Π΄ΠΈΡΠΏΠ΅ΡΡΠΈΠΎΠ½Π½Π°Ρ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎ-ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½Π°Ρ ΠΌΠΈΠΊΡΠΎΡΠΊΡΡΡΠ°ΠΊΡΠΈΡ, ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΠ΅ Π³ΠΎΡΠΌΠΎΠ½Ρ, ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΡΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅Π·DOI: http://dx.doi.org/10.15826/analitika.2018.22.3.01
ΠΠΠΠΠΠ‘ΠΠΠΠ’Π ΠΠ§ΠΠ‘ΠΠΠ ΠΠΠΠ’Π ΠΠΠ¬ Π‘ΠΠ ΠΠ¦ΠΠ ΠΠΠΠΠΠ ΠΠ Π ΠΠ‘ΠΠΠΠ¬ΠΠΠΠΠΠΠ PLOT-ΠΠΠΠΠΠΠ Π‘ ΠΠΠΠΠ ΠΠ’ΠΠΠ Π‘Π’ΠΠ¦ΠΠΠΠΠ ΠΠΠ Π€ΠΠΠΠ
The article is related to the investigation of adsorptionΒ potential of proteins (albumin, insulin,Β lysozyme andΒ myoglobin)Β on the surfaceΒ of hyperbranchedΒ polymers, specifically, water-soluble oligosaccharide derivatives of polyethyleneimine, which are used as a stationery phase inΒ capillaryΒ electrochromatography (CEC). Various protein molecules are known to be markers of different diseases. Detection and quantification of these proteins are of the highest importance for a successful disease diagnostics. However, irreversible adsorption of proteins onto the walls of the silica-fused capillary during the separation process may distort the results of the analysis. A method of ellipsometry is proposed to solve the problem. In the research we suggest to carry out the ellipsometric measurement mode in situ on the surface of a silicon wafer coated with a thin film of hyperbranched polyethyleneimine modified with maltose. According to the data of ellipsometric investigation, hyperbranched polymers are revealed to prevent protein adsorption during their electrophoretic separation.Key words: Β hyperbranchedΒ polyethyleneimine, ellipsometry,Β proteinΒ adsorption, capillaryΒ electrochromatography, PLOT-column.(Russian)DOI:Β http://dx.doi.org/10.15826/analitika.2014.18.1.009Β V. Potolitsyna, L. Kartsova, E. Bessonova Β Saint-Petersburg State University (SPbU),Β St. Petersburg, Russian FederationΒ ΠΠ΅ΡΠΎΠ΄ΠΎΠΌ ΡΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΠΈ ΠΈΠ·ΡΡΠ΅Π½Π° Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΡ ΡΠΎΡΠ±ΡΠΈΠΈ Π±Π΅Π»ΠΊΠΎΠ² (Π°Π»ΡΠ±ΡΠΌΠΈΠ½, ΠΈΠ½ΡΡΠ»ΠΈΠ½, Π»ΠΈΠ·ΠΎΡΠΈΠΌ ΠΈ ΠΌΠΈΠΎΠ³Π»ΠΎΠ±ΠΈΠ½) Π½Π° ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ ΡΠ²Π΅ΡΡ
ΡΠ°Π·Π²Π΅ΡΠ²Π»Π΅Π½Π½ΡΡ
ΠΏΠΎΠ»ΠΈΠΌΠ΅ΡΠΎΠ² (Π‘Π Π) β Π²ΠΎΠ΄ΠΎΡΠ°ΡΡΠ²ΠΎΡΠΈΠΌΡΡ
ΠΎΠ»ΠΈΠ³ΠΎΡΠ°Ρ
Π°ΡΠΈΠ΄Π½ΡΡ
ΠΏΡΠΎΠΈΠ·Π²ΠΎΠ΄Π½ΡΡ
ΠΏΠΎΠ»ΠΈΡΡΠΈΠ»Π΅Π½ΠΈΠΌΠΈΠ½Π° (PEI-Mal), ΠΈΡΠΏΠΎΠ»ΡΠ·ΡΠ΅ΠΌΡΡ
Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΡΡΠ°ΡΠΈΠΎΠ½Π°ΡΠ½ΠΎΠΉ ΡΠ°Π·Ρ Π² ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠΠ₯). ΠΠ·Π²Π΅ΡΡΠ½ΠΎ, ΡΡΠΎ ΠΌΠ½ΠΎΠ³ΠΈΠ΅ Π±Π΅Π»ΠΊΠΎΠ²ΡΠ΅ ΠΌΠΎΠ»Π΅ΠΊΡΠ»Ρ ΡΠ²Π»ΡΡΡΡΡ ΠΌΠ°ΡΠΊΠ΅ΡΠ°ΠΌΠΈ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
Π·Π°Π±ΠΎΠ»Π΅Π²Π°Π½ΠΈΠΉ, ΠΏΠΎΡΡΠΎΠΌΡ Π΄Π»Ρ ΡΡΠΏΠ΅ΡΠ½ΠΎΠΉ Π΄ΠΈΠ°Π³Π½ΠΎΡΡΠΈΠΊΠΈ ΡΡΠΈΡ
Π·Π°Π±ΠΎΠ»Π΅Π²Π°Π½ΠΈΠΉ Π½Π΅ΠΎΠ±Ρ
ΠΎΠ΄ΠΈΠΌΠΎ ΠΈΡ
ΡΠΎΡΠ½ΠΎΠ΅ ΠΊΠΎΠ»ΠΈΡΠ΅ΡΡΠ²Π΅Π½Π½ΠΎΠ΅ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠ΅, Π° Π½Π΅ΠΎΠ±ΡΠ°ΡΠΈΠΌΠ°Ρ Π°Π΄ΡΠΎΡΠ±ΡΠΈΡ Π±Π΅Π»ΠΊΠΎΠ² Π½Π° ΡΡΠ΅Π½ΠΊΠ°Ρ
ΠΊΠ²Π°ΡΡΠ΅Π²ΠΎΠ³ΠΎ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° Π² ΠΏΡΠΎΡΠ΅ΡΡΠ΅ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ ΠΌΠΎΠΆΠ΅Ρ ΠΈΡΠΊΠ°ΠΆΠ°ΡΡ ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΡ Π°Π½Π°Π»ΠΈΠ·Π°, ΠΏΠΎΡΡΠΎΠΌΡ Π·Π½Π°Π½ΠΈΠ΅ ΠΎΡΠΎΠ±Π΅Π½Π½ΠΎΡΡΠ΅ΠΉ ΠΏΡΠΎΡΠ΅ΡΡΠΎΠ² Π°Π΄ΡΠΎΡΠ±ΡΠΈΠΈ Π±Π΅Π»ΠΊΠΎΠ² Π½Π° ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΡΡ
Π²Π΅ΡΡΠΌΠ° Π°ΠΊΡΡΠ°Π»ΡΠ½ΠΎ.Π ΡΠ°Π±ΠΎΡΠ΅ Π΄Π»Ρ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΈΡ Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΠΉ Π°Π΄ΡΠΎΡΠ±ΡΠΈΠΈ Π±Π΅Π»ΠΊΠΎΠ² Π²ΡΠ±ΡΠ°Π½ ΠΌΠ΅ΡΠΎΠ΄ ΡΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΠΈ ΠΊΠ°ΠΊ Π²ΡΡΠΎΠΊΠΎΡΡΠ²ΡΡΠ²ΠΈΡΠ΅Π»ΡΠ½ΡΠΉ, Π±ΡΡΡΡΠΎΠ΄Π΅ΠΉΡΡΠ²ΡΡΡΠΈΠΉ ΠΈ Π±Π΅ΡΠΊΠΎΠ½ΡΠ°ΠΊΡΠ½ΡΠΉ. ΠΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΡ Π½Π΅ΠΎΠ΄Π½ΠΎΠΊΡΠ°ΡΠ½ΠΎ ΠΈ ΡΡΠΏΠ΅ΡΠ½ΠΎ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π»Π°ΡΡ ΡΠ°Π·Π»ΠΈΡΠ½ΡΠΌΠΈ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°ΡΠ΅Π»ΡΠΌΠΈ Π΄Π»Ρ ΠΈΠ·ΡΡΠ΅Π½ΠΈΡ Π°Π΄ΡΠΎΡΠ±ΡΠΈΠΈ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
Π²Π΅ΡΠ΅ΡΡΠ² ΠΈΠ· Π³Π°Π·ΠΎΠ²ΠΎΠΉ ΠΈ ΠΈΠ· ΠΆΠΈΠ΄ΠΊΠΎΠΉ ΡΠ°Π·. Π ΡΠ°Π±ΠΎΡΠ΅ ΠΏΡΠΎΠ²Π΅Π΄Π΅Π½Ρ ΡΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΈΠ·ΠΌΠ΅ΡΠ΅Π½ΠΈΡ Π² ΡΠ΅ΠΆΠΈΠΌΠ΅ in situ Π½Π° ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ ΠΊΡΠ΅ΠΌΠ½ΠΈΠ΅Π²ΠΎΠΉ ΠΏΠ»Π°ΡΡΠΈΠ½Ρ, ΠΏΠΎΠΊΡΡΡΠΎΠΉ ΡΠΎΠ½ΠΊΠΎΠΉ ΠΏΠ»Π΅Π½ΠΊΠΎΠΉ ΡΠ²Π΅ΡΡ
ΡΠ°Π·Π²Π΅ΡΠ²Π»Π΅Π½Π½ΠΎΠ³ΠΎ ΠΏΠΎΠ»ΠΈΡΡΠΈΠ»Π΅Π½ΠΈΠΌΠΈΠ½Π°, ΠΌΠΎΠ΄ΠΈΡΠΈΡΠΈΡΠΎΠ²Π°Π½Π½ΠΎΠ³ΠΎ ΠΌΠ°Π»ΡΡΠΎΠ·ΠΎΠΉ. ΠΠ΅ΡΠΎΠ΄ΠΎΠΌ ΡΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΠΈ ΡΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π‘Π Π ΠΏΡΠ΅ΠΏΡΡΡΡΠ²ΡΠ΅Ρ Π°Π΄ΡΠΎΡΠ±ΡΠΈΠΈ Π±Π΅Π»ΠΊΠΎΠ² Π½Π° ΡΡΠ΅Π½ΠΊΠ°Ρ
ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠΉ ΠΊΠΎΠ»ΠΎΠ½ΠΊΠΈ ΠΏΡΠΈ ΠΈΡ
ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠΈ Π² ΡΡΠ»ΠΎΠ²ΠΈΡΡ
ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ.ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: ΠΌΠ°Π»ΡΡΠΎΠ·ΠΈΠ»ΠΈΡΠΎΠ²Π°Π½Π½ΡΠΉ ΡΠ²Π΅ΡΡ
ΡΠ°Π·Π²Π΅ΡΠ²Π»Π΅Π½Π½ΡΠΉ ΠΏΠΎΠ»ΠΈΡΡΠΈΠ»Π΅Π½ΠΈΠΌΠΈΠ½, ΡΠ»Π»ΠΈΠΏΡΠΎΠΌΠ΅ΡΡΠΈΡ, Π°Π΄ΡΠΎΡΠ±ΡΠΈΡ Π±Π΅Π»ΠΊΠΎΠ², ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½Π°Ρ ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡ, PLOT-ΠΊΠΎΠ»ΠΎΠ½ΠΊΠΈ.DOI:Β http://dx.doi.org/10.15826/analitika.2014.18.1.009
ΠΠΠΠΠ₯Π ΠΠΠΠ’ΠΠΠ ΠΠ€ΠΠ§ΠΠ‘ΠΠΠ ΠΠΠ ΠΠΠΠΠΠΠΠ ΠΠ‘ΠΠΠ ΠΠΠΠΠ β ΠΠ ΠΠΠ£ΠΠ’Π ΠΠΠΠΠΠΠΠΠΠ‘Π’ΠΠΠ― Π‘ΠΠΠΠΠΠ’ΠΠΠΠ ΠΠΠ‘ΠΠΠ ΠΠΠ Π‘ Ξ±-Π’ΠΠ ΠΠΠΠΠΠΠ
The reaction product of singlet oxygen with Ξ±-terpinene, ascaridole, can be used in an indirect gas chromatographic determination of the singlet oxygen mass concentration in the air. However, ascaridole is a thermally unstable compound, which can isomerize due to high temperature exposure during the analysis.Thermal decomposition products of ascaridole were identified by gas chromatography-mass spectrometry: isoascaridole, 1,2-ethoxy-p-menthane-3-one and 3,4-ethoxy-p-menthane-2-one. The discrepancy between obtained mass spectrum of ascaridole and mass spectra shown in NIST databases was found. The dependence of ascaridole signal intensity from temperature of injector and detector and from column conditioning was established. These conditions were investigated and optimized.Key words: ascaridole, singlet oxygen, gas chromatography, gas chromatography-mass spectrometry(Russian)DOI:Β http://dx.doi.org/10.15826/analitika.2013.17.4.009A.S. Ovechkin1,2, M.D. Reyngeverts2, L.A. Kartsova11St. Petersburg State University,Β Petergof, St. Petersburg, Russian Federation2FSUE Β«RSC Β«Applied ChemistryΒ», St. Petersburg, Russian FederationΠΡΠΎΠ΄ΡΠΊΡ Π²Π·Π°ΠΈΠΌΠΎΠ΄Π΅ΠΉΡΡΠ²ΠΈΡ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠ³ΠΎ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄Π° Ρ Ξ±-ΡΠ΅ΡΠΏΠΈΠ½Π΅Π½ΠΎΠΌ, Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ», ΠΌΠΎΠΆΠ΅Ρ Π±ΡΡΡ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ ΠΏΡΠΈ ΠΊΠΎΡΠ²Π΅Π½Π½ΠΎΠΌ Π³Π°Π·ΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠΈ ΠΌΠ°ΡΡΠΎΠ²ΠΎΠΉ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΠΈ ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΠΎΠ³ΠΎ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄Π° Π² Π²ΠΎΠ·Π΄ΡΡ
Π΅. ΠΠ΄Π½Π°ΠΊΠΎ Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ» β ΡΠ΅ΡΠΌΠΈΡΠ΅ΡΠΊΠΈ Π½Π΅ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΠ΅ ΡΠΎΠ΅Π΄ΠΈΠ½Π΅Π½ΠΈΠ΅, ΡΠΏΠΎΡΠΎΠ±Π½ΠΎΠ΅ ΠΈΠ·ΠΎΠΌΠ΅ΡΠΈΠ·ΠΎΠ²Π°ΡΡΡΡ ΠΏΠΎΠ΄ Π΄Π΅ΠΉΡΡΠ²ΠΈΠ΅ΠΌ ΡΠ΅ΠΌΠΏΠ΅ΡΠ°ΡΡΡΡ Π² Ρ
ΠΎΠ΄Π΅ Π°Π½Π°Π»ΠΈΠ·Π°.ΠΠ΅ΡΠΎΠ΄ΠΎΠΌ Ρ
ΡΠΎΠΌΠ°ΡΠΎ-ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠΎΠΌΠ΅ΡΡΠΈΠΈ ΠΈΠ΄Π΅Π½ΡΠΈΡΠΈΡΠΈΡΠΎΠ²Π°Π½Ρ ΠΏΡΠΎΠ΄ΡΠΊΡΡ ΡΠ΅ΡΠΌΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΡΠ°Π·Π»ΠΎΠΆΠ΅Π½ΠΈΡ Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ»Π°: ΠΈΠ·ΠΎΠ°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ», 1,2-ΡΡΠΎΠΊΡΠΈ-ΠΏ-ΠΌΠ΅Π½ΡΠ°Π½-3-ΠΎΠ½ ΠΈ 3,4-ΡΡΠΎΠΊΡΠΈ-ΠΏ-ΠΌΠ΅Π½ΡΠ°Π½-2-ΠΎΠ½. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ Π½Π΅ΡΠΎΠΎΡΠ²Π΅ΡΡΡΠ²ΠΈΠ΅ ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠ° Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ»Π°, ΠΏΠΎΠ»ΡΡΠ΅Π½Π½ΠΎΠ³ΠΎ Π² Π½Π°ΡΡΠΎΡΡΠ΅ΠΉ ΡΠ°Π±ΠΎΡΠ΅, ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠ°ΠΌ, ΠΏΡΠΈΠ²Π΅Π΄Π΅Π½Π½ΡΠΌ Π² Π±Π°Π·Π°Ρ
Π΄Π°Π½Π½ΡΡ
NIST. ΠΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½Ρ ΠΈ ΠΎΠΏΡΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ Π³Π°Π·ΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ»Π°: ΡΠ΅ΠΌΠΏΠ΅ΡΠ°ΡΡΡΡ ΠΈΡΠΏΠ°ΡΠΈΡΠ΅Π»Ρ ΠΈ Π΄Π΅ΡΠ΅ΠΊΡΠΎΡΠ°, Π½Π΅ΠΎΠ±Ρ
ΠΎΠ΄ΠΈΠΌΠΎΡΡΡ ΠΊΠΎΠ½Π΄ΠΈΡΠΈΠΎΠ½ΠΈΡΠΎΠ²Π°Π½ΠΈΡ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΎΠΉ ΠΊΠΎΠ»ΠΎΠ½ΠΊΠΈ ΠΈ ΠΏΠ°ΡΠ°ΠΌΠ΅ΡΡΡ Π΅Π³ΠΎ ΠΏΡΠΎΠ²Π΅Π΄Π΅Π½ΠΈΡ.ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°:Π°ΡΠΊΠ°ΡΠΈΠ΄ΠΎΠ», ΡΠΈΠ½Π³Π»Π΅ΡΠ½ΡΠΉ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄, Π³Π°Π·ΠΎΠ²Π°Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡ, Ρ
ΡΠΎΠΌΠ°ΡΠΎ-ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠΎΠΌΠ΅ΡΡΠΈΡDOI:Β http://dx.doi.org/10.15826/analitika.2013.17.4.00
Π₯Π ΠΠΠΠ’ΠΠΠ ΠΠ€ΠΠ§ΠΠ‘ΠΠΠ Π Π₯Π ΠΠΠΠ’Π-ΠΠΠ‘Π‘-Π‘ΠΠΠΠ’Π ΠΠΠΠ’Π ΠΠ§ΠΠ‘ΠΠΠ ΠΠΠ ΠΠΠΠΠΠΠΠ ΠΠ ΠΠ’ΠΠΠΠ’Π£ΠΠΠ ΠΠ£ΠΠΠΠΠ«Π₯ ΠΠ ΠΠΠΠ ΠΠ’ΠΠ ΠΠ‘ΠΠΠΠΠΠΠ Π Π―ΠΠ Π ΠΠΠΠΠΠ ΠΠ ΠΠΠ
In the current study the possibility of the simultaneous determination of anti-tuberculosis (anti-TB) drugs (isoniazid, pyrazinamide, ethambutol and rifampicin) using the reversed-phase HPLC (RP-HPLC) and ion-pair chromatography was investigated. A selective and highly sensitive liquid chromatography/tandem mass spectrometry method for the simultaneous determination of four anti-TB drugs (isoniazid, pyrazinamide, ethambutol and rifampicin) in the human plasma was developed. The detection was carried out using the multiple reaction-monitoring (MRM) modes with positive polarity. The fragmentation conditions for each drug were optimized, and the conditions for the blood plasma preparation for HPLC/MS analysis, including the protein precipitation with ACN with a ratio of 3:1 (by volume), were chosen. The matrix effects on the separation and ionization of anti-TB drugs were estimated by the post-extraction additives method. It was shown that the 10-fold dilution of plasma extracts was sufficient to decrease the influence of the sample matrix. The stability of anti-TB drugs during the analysis (in autosampler at 1 and 12 hours) and at storage conditions (3 cycles of freeze-thaw) was studied. The method for increasing the stability of rifampicin using ascorbic acid (1 mg/ml) as antioxidant was provided. The LOD with UV detection were 2 β 20 Β΅g/ml, in SIM-mode β 2 β 15 ng/ml and in MRM-mode β 0.5 β 10 ng/ml respectively. The possibility of the determination of four anti-TB drugs in real plasma samples of patients with tuberculosis undergoing drug therapy in optimized conditions HPLC/MC was shown.Key words: anti-tuberculosis drugs, RP HPLC, LC/MS/MS, matrix effect(Russian)DOI: http://dx.doi.org/10.15826/analitika.2016.20.2.007Β E.A. Bessonova, L.A. Kartsova, S.A. Soloveva Saint-Petersburg State University, 7/9 Universitetskaya nab., St. Petersburg, 199034, Russian FederationΠ ΡΠ°Π±ΠΎΡΠ΅ Π²ΡΡΠ²Π»Π΅Π½Ρ Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΠΈ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΠ΅ΡΡΡΠ΅Ρ
ΠΏΡΠΎΡΠΈΠ²ΠΎΡΡΠ±Π΅ΡΠΊΡΠ»Π΅Π·Π½ΡΡ
ΠΏΡΠ΅ΠΏΠ°ΡΠ°ΡΠΎΠ² (ΠΠ’Π) Β (ΡΡΠ°ΠΌΠ±ΡΡΠΎΠ», ΠΏΠΈΡΠ°Π·ΠΈΠ½Π°ΠΌΠΈΠ΄, ΠΈΠ·ΠΎΠ½ΠΈΠ°Π·ΠΈΠ΄, ΡΠΈΡΠ°ΠΌΠΏΠΈΡΠΈΠ½) ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΎΠ±ΡΠ°ΡΡΠ½Π½ΠΎ-ΡΠ°Π·ΠΎΠ²ΠΎΠΉ ΠΠΠΠ₯ (ΠΠ€ ΠΠΠΠ₯) ΠΈ ΠΈΠΎΠ½-ΠΏΠ°ΡΠ½ΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ.Β ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ Π²Π°ΡΠΈΠ°Π½Ρ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΡΠΈΡ
ΠΠ’Π Π² ΠΏΠ»Π°Π·ΠΌΠ΅ ΠΊΡΠΎΠ²ΠΈ ΡΠ΅Π»ΠΎΠ²Π΅ΠΊΠ° ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΠ€ ΠΠΠΠ₯ Ρ ΡΠ°Π½Π΄Π΅ΠΌΠ½ΡΠΌ ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠΌ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Ρ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΏΡΠ΅ΠΉ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΠ΅ΠΉ. ΠΠ΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΎΡΡΡΠ΅ΡΡΠ²Π»ΡΠ»ΠΈ Π² ΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΏΠΎΠ»ΠΎΠΆΠΈΡΠ΅Π»ΡΠ½ΠΎΠΉ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΠΈ ΠΏΡΡΡΠΌ ΠΌΠΎΠ½ΠΈΡΠΎΡΠΈΠ½Π³Π° ΠΌΠ½ΠΎΠΆΠ΅ΡΡΠ²Π΅Π½Π½ΡΡ
ΡΠ΅Π°ΠΊΡΠΈΠΉ (MRM). ΠΠΏΡΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ ΡΡΠ°Π³ΠΌΠ΅Π½ΡΠ°ΡΠΈΠΈ Π΄Π»Ρ ΠΊΠ°ΠΆΠ΄ΠΎΠ³ΠΎ Π»Π΅ΠΊΠ°ΡΡΡΠ²Π΅Π½Π½ΠΎΠ³ΠΎ Π²Π΅ΡΠ΅ΡΡΠ²Π°. ΠΠ°ΠΉΠ΄Π΅Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ ΠΏΠΎΠ΄Π³ΠΎΡΠΎΠ²ΠΊΠΈ ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ ΠΊ ΠΠΠΠ₯/ΠΠ‘ Π°Π½Π°Π»ΠΈΠ·Ρ, Π²ΠΊΠ»ΡΡΠ°ΡΡΠΈΠ΅ ΠΎΡΠ°ΠΆΠ΄Π΅Π½ΠΈΠ΅ Π±Π΅Π»ΠΊΠΎΠ² ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ Π°ΡΠ΅ΡΠΎΠ½ΠΈΡΡΠΈΠ»ΠΎΠΌ. ΠΠ½Π°ΡΠ΅Π½ΠΈΡ ΡΡΠ΅ΠΏΠ΅Π½Π΅ΠΉ ΠΈΠ·Π²Π»Π΅ΡΠ΅Π½ΠΈΡ ΠΠ’Π ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ 85-90 %. ΠΡΠΎΠ²Π΅Π΄Π΅Π½Π° ΠΎΡΠ΅Π½ΠΊΠ° Π²Π»ΠΈΡΠ½ΠΈΡ ΠΌΠ°ΡΡΠΈΡΡ ΠΏΡΠΎΠ±Ρ Π½Π° ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠ΅ ΠΈ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΡ ΠΠ’Π ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΏΠΎΡΡ-ΡΠΊΡΡΡΠ°ΠΊΡΠΈΠΎΠ½Π½ΠΎΠΉ Π΄ΠΎΠ±Π°Π²ΠΊΠΈ. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΡΠ°Π·Π±Π°Π²Π»Π΅Π½ΠΈΠ΅ ΡΠΊΡΡΡΠ°ΠΊΡΠ° ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ Π² 10 ΡΠ°Π· Π΄ΠΎΡΡΠ°ΡΠΎΡΠ½ΠΎ Π΄Π»Ρ ΡΡΠ΅Π±ΡΠ΅ΠΌΠΎΠ³ΠΎ ΡΠ½ΠΈΠΆΠ΅Π½ΠΈΡ ΠΌΠ°ΡΡΠΈΡΠ½ΠΎΠ³ΠΎ ΡΡΡΠ΅ΠΊΡΠ°. Β ΠΠ·ΡΡΠ΅Π½Π° ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΡ ΠΠ’Π Π² ΠΏΡΠΎΡΠ΅ΡΡΠ΅ Π°Π½Π°Π»ΠΈΠ·Π° (Π°Π²ΡΠΎΡΠ°ΠΌΠΏΠ»Π΅Ρ 1 ΠΈ 12 Ρ.) ΠΈ Π² ΡΡΠ»ΠΎΠ²ΠΈΡΡ
Ρ
ΡΠ°Π½Π΅Π½ΠΈΡ (3 ΡΠΈΠΊΠ»Π° Π·Π°ΠΌΠΎΡΠΎΠ·ΠΊΠ°-ΡΠ°Π·ΠΌΠΎΡΠΎΠ·ΠΊΠ°). ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ ΡΠΏΠΎΡΠΎΠ± ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΡ ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΠΈ ΡΠΈΡΠ°ΠΌΠΏΠΈΡΠΈΠ½Π° Ρ Π΄ΠΎΠ±Π°Π²Π»Π΅Π½ΠΈΠ΅ΠΌ Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ Π°Π½ΡΠΈΠΎΠΊΡΠΈΠ΄Π°Π½ΡΠ° Π°ΡΠΊΠΎΡΠ±ΠΈΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ (1 ΠΌΠ³/ΠΌΠ»). ΠΡΠ΅Π΄Π΅Π»Ρ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ Ρ Π£Π€ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ ΠΎΡ 2 Π΄ΠΎ 20 ΠΌΠΊΠ³/ΠΌΠ», Ρ ΠΠ‘ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Π² SIMβΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΎΡ 2 Π΄ΠΎ 15 Π½Π³/ΠΌΠ» ΠΈ Π² MRMβΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΎΡ 0.5 Π΄ΠΎ 10 Π½Π³/ΠΌΠ». Π ΠΎΠΏΡΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Π½ΡΡ
ΡΡΠ»ΠΎΠ²ΠΈΡΡ
ΠΏΠΎΠΊΠ°Π·Π°Π½Π° Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΡ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ ΠΈ ΠΊΠΎΠ»ΠΈΡΠ΅ΡΡΠ²Π΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ Π²ΡΠ΅Ρ
ΡΠ΅ΡΡΡΠ΅Ρ
ΠΠ’Π Π² ΠΏΠ»Π°Π·ΠΌΠ΅ ΠΊΡΠΎΠ²ΠΈ Π±ΠΎΠ»ΡΠ½ΠΎΠ³ΠΎ ΡΡΠ±Π΅ΡΠΊΡΠ»Π΅Π·ΠΎΠΌ Ρ ΠΏΡΠΎΠ²ΠΎΠ΄ΠΈΠΌΠΎΠΉ Π»Π΅ΠΊΠ°ΡΡΡΠ²Π΅Π½Π½ΠΎΠΉ ΡΠ΅ΡΠ°ΠΏΠΈΠ΅ΠΉ. ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: ΠΏΡΠΎΡΠΈΠ²ΠΎΡΡΠ±Π΅ΡΠΊΡΠ»ΡΠ·Π½ΡΠ΅ ΠΏΡΠ΅ΠΏΠ°ΡΠ°ΡΡ, ΠΠ€ ΠΠΠΠ₯, ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΎΠ΅ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅, ΠΌΠ°ΡΡΠΈΡΠ½ΡΠΉ ΡΡΡΠ΅ΠΊΡ, ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΡ ΡΠΈΡΠ°ΠΌΠΏΠΈΡΠΈΠ½Π°DOI: http://dx.doi.org/10.15826/analitika.2016.20.2.00
Π ΠΠΠΠΠΠΠΠΠ Π‘Π’ΠΠ ΠΠΠΠΠ«Π₯ ΠΠΠ ΠΠΠΠΠ ΠΠΠ’ΠΠΠΠ ΠΠΠΠ ΠΠΠΠ£ΠΠ¬Π‘ΠΠΠΠΠΠ ΠΠΠΠΠ’Π ΠΠΠΠΠΠ’ΠΠ§ΠΠ‘ΠΠΠ Π₯Π ΠΠΠΠ’ΠΠΠ ΠΠ€ΠΠ Π‘ Π£Π§ΠΠ‘Π’ΠΠΠ ΠΠΠΠΠ«Π₯ ΠΠΠΠΠΠ‘Π’ΠΠ
Microemulsion electrokinetic chromatography (MEEKC) is a promising method for separating ionic and neutral analytes in the complex matrix, where a microemulsion is used as the background electrolyte. Current work identified the possibility of using hydrophilic ionic liquids (ILs) based on imidazole (C12MImCl, C16MImCl) as modifiers and surfactants, as well as hydrophobic ILs (C6MImBF4) as an βoilβ in the microemulsion for the separation of steroid hormones by MEEKC. The factors such as ILs concentration, nature and pH of the background electrolyte, and the ratio of the components of the microemulsion, that influence the efficiency and separation selectivity of analytes were found. Suitable conditions for the complete separation of a model mixture of steroid hormones: cortisol, cortisone, 11-deoxycortisol, 11-deoxycorticosterone, corticosterone were obtained. The analytical characteristics of methods (optimized conditions) for the determination of steroids by micellar and microemulsion electrokinetic chromatography were compared. It was investigated that the addition of 15 mM 2-hydroxypropyl-Ξ²-cyclodextrin increases the separation selectivity and reduces the analysis time. The application of the on-line concentration methods made it possible to reduce the detection limits of analytes to 50 ng / ml.Β The mode for electrophoretic determination of steroid hormones in biological fluids (urine, blood serum) by MEEKC with the use of ionic liquids has been proposed using the previously obtained results.Β Β Β Β Β Β Β Β Keywords: imidazolium ionic liquids, steroid hormones, microemulsion electrokinetic chromatography, microemulsionDOI: http://dx.doi.org/10.15826/analitika.2019.23.2.001(Russian)L.A. Kartsova, E.A. Bessonova, D.O. Moskvichev Saint-Petersburg State University, Institute of Chemistry, 26 Universitetskii prospect, St. Petersburg, Petergof, 198504, Russian FederationΒ Π ΡΠ°Π±ΠΎΡΠ΅ Π²ΡΡΠ²Π»Π΅Π½Ρ ΠΏΠ΅ΡΡΠΏΠ΅ΠΊΡΠΈΠ²Ρ ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ΠΈΡ Π³ΠΈΠ΄ΡΠΎΡΠΈΠ»ΡΠ½ΡΡ
ΠΈΠΎΠ½Π½ΡΡ
ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ΅ΠΉ (ΠΠ) Π½Π° ΠΎΡΠ½ΠΎΠ²Π΅ ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»Π° (C12MImCl, C16MImCl) Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΠΌΠΎΠ΄ΠΈΡΠΈΠΊΠ°ΡΠΎΡΠΎΠ² ΠΈ ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠ½ΠΎ-Π°ΠΊΡΠΈΠ²Π½ΡΡ
Π²Π΅ΡΠ΅ΡΡΠ² (ΠΠΠ), Π° ΡΠ°ΠΊΠΆΠ΅ Π³ΠΈΠ΄ΡΠΎΡΠΎΠ±Π½ΡΡ
ΠΠ (C6MImBF4) ΠΊΠ°ΠΊ Β«ΠΌΠ°ΡΠ»Π°Β» Π² ΡΠΎΡΡΠ°Π²Π΅ ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΠΈ ΠΏΡΠΈ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠΈ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ² ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΠΎΠ½Π½ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠΠΠΠ₯). ΠΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΡΒ ΡΠ°ΠΊΡΠΎΡΡ (ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΡ ΠΈΠΎΠ½Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠΈ, ΠΏΡΠΈΡΠΎΠ΄Π° ΠΈ Π·Π½Π°ΡΠ΅Π½ΠΈΠ΅ ΡΠ ΡΠΎΠ½ΠΎΠ²ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΠ°, ΡΠΎΠΎΡΠ½ΠΎΡΠ΅Π½ΠΈΠ΅ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
ΠΊΠΎΠΌΠΏΠΎΠ½Π΅Π½ΡΠΎΠ² ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΠΈ), Π²Π»ΠΈΡΡΡΠΈΠ΅ Π½Π° ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡ ΠΈ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ Π°Π½Π°Π»ΠΈΡΠΎΠ². ΠΠ°ΠΉΠ΄Π΅Π½Ρ ΠΏΠΎΠ΄Ρ
ΠΎΠ΄ΡΡΠΈΠ΅ ΡΡΠ»ΠΎΠ²ΠΈΡ Π΄Π»Ρ ΠΏΠΎΠ»Π½ΠΎΠ³ΠΎ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ ΠΌΠΎΠ΄Π΅Π»ΡΠ½ΠΎΠΉ ΡΠΌΠ΅ΡΠΈ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ²: ΠΊΠΎΡΡΠΈΠ·ΠΎΠ»Π°, ΠΊΠΎΡΡΠΈΠ·ΠΎΠ½Π°, 11-Π΄Π΅Π·ΠΎΠΊΡΠΈΠΊΠΎΡΡΠΈΠ·ΠΎΠ»Π°, 11-Π΄Π΅Π·ΠΎΠΊΡΠΈΠΊΠΎΡΡΠΈΠΊΠΎΡΡΠ΅ΡΠΎΠ½Π°, 11-Π΄Π΅Π³ΠΈΠ΄ΡΠΎΠΊΠΎΡΡΠΈΠΊΠΎΡΡΠ΅ΡΠΎΠ½Π°. ΠΡΠΎΠ²Π΅Π΄Π΅Π½ΠΎ ΡΠΎΠΏΠΎΡΡΠ°Π²Π»Π΅Π½ΠΈΠ΅ Π°Π½Π°Π»ΠΈΡΠΈΡΠ΅ΡΠΊΠΈΡ
Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠ² ΠΌΠΈΡΠ΅Π»Π»ΡΡΠ½ΠΎΠΉ ΠΈ ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΠΎΠ½Π½ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ Β ΠΏΡΠΈ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠΈ ΡΡΠ΅ΡΠΎΠΈΠ΄ΠΎΠ². ΠΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΎ, ΡΡΠΎ Π΄ΠΎΠ±Π°Π²ΠΊΠ° 15 ΠΌΠ 2-Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΏΡΠΎΠΏΠΈΠ»-Ξ²-ΡΠΈΠΊΠ»ΠΎΠ΄Π΅ΠΊΡΡΡΠΈΠ½Π° ΠΏΡΠΈΠ²Π΅Π»Π° ΠΊ ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΡ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΠΈ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ, ΠΈ ΠΏΡΠΈ ΡΡΠΎΠΌ Π²ΡΠ΅ΠΌΡ Π°Π½Π°Π»ΠΈΠ·Π° ΡΠΌΠ΅Π½ΡΡΠΈΠ»ΠΎΡΡ.Β ΠΡΠΈΠΌΠ΅Π½Π΅Π½ΠΈΠ΅ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠ² on-line ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΏΠΎΠ·Π²ΠΎΠ»ΠΈΠ»ΠΎ ΡΠ½ΠΈΠ·ΠΈΡΡ ΠΏΡΠ΅Π΄Π΅Π»Ρ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ Π°Π½Π°Π»ΠΈΡΠΎΠ² Π΄ΠΎ 50 Π½Π³/ΠΌΠ». ΠΠ° ΠΎΡΠ½ΠΎΠ²Π°Π½ΠΈΠΈ ΠΏΠΎΠ»ΡΡΠ΅Π½Π½ΡΡ
ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΠΎΠ² ΠΏΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ ΡΠΊΡΠΏΡΠ΅ΡΡΠ½ΡΠΉ ΡΠΏΠΎΡΠΎΠ± ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΡ
Π³ΠΎΡΠΌΠΎΠ½ΠΎΠ² Π² ΠΎΠ±ΡΠ°Π·ΡΠ°Ρ
ΠΌΠΎΡΠΈ ΠΈ ΡΡΠ²ΠΎΡΠΎΡΠΊΠΈΒ ΠΊΡΠΎΠ²ΠΈ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ Β ΠΠΠΠΠ₯ Ρ Π²Π²Π΅Π΄Π΅Π½ΠΈΠ΅ΠΌ ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»ΠΈΠ΅Π²ΠΎΠΉ ΠΈΠΎΠ½Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠΈ Π² ΡΠΎΡΡΠ°Π² ΡΠΎΠ½ΠΎΠ²ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΠ°.ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: Β ΠΈΠΌΠΈΠ΄Π°Π·ΠΎΠ»ΠΈΠ΅Π²ΡΠ΅ ΠΈΠΎΠ½Π½ΡΠ΅ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠΈ, ΡΡΠ΅ΡΠΎΠΈΠ΄Π½ΡΠ΅ Π³ΠΎΡΠΌΠΎΠ½Ρ, ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΠΎΠ½Π½Π°Ρ ΡΠ»Π΅ΠΊΡΡΠΎΠΊΠΈΠ½Π΅ΡΠΈΡΠ΅ΡΠΊΠ°Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠΎΡΠΈΡ, ΠΌΠΈΠΊΡΠΎΡΠΌΡΠ»ΡΡΠΈΡDOI: http://dx.doi.org/10.15826/analitika.2019.23.2.00
ΠΠΠ ΠΠΠΠΠΠΠΠ ΠΠ ΠΠΠΠΠ§ΠΠ‘ΠΠΠ₯ ΠΠΠ‘ΠΠΠ’, Π£ΠΠΠΠΠΠΠΠ Π ΠΠΠΠ‘ΠΠΠ‘Π’ΠΠ’ΠΠΠΠ Π ΠΠΠ©ΠΠΠ«Π₯ ΠΠ ΠΠΠ£ΠΠ’ΠΠ₯ Π ΠΠΠΠΠΠΠΠ§ΠΠ‘ΠΠ ΠΠΠ’ΠΠΠΠ«Π₯ ΠΠΠΠΠΠΠΠ₯ ΠΠΠ’ΠΠΠΠ ΠΠ«Π‘ΠΠΠΠΠ€Π€ΠΠΠ’ΠΠΠΠΠ ΠΠΠΠΠΠ‘Π’ΠΠΠ Π₯Π ΠΠΠΠ’ΠΠΠ ΠΠ€ΠΠ
The content of organic acids and carbohydrates in samples of wine, juice, dairy products, dietary supplements was revealed by reverse-phase high performance liquid chromatography (HPLC). Organic acids (oxalic acid, tartaric acid, formic acid, malic acid, lactic acid, acetic acid, citric acid, succinic acid, fumaric acid, propionic acid) was determined by using spectrophotometric detection, carbohydrates (glucose, lactose, maltose, mannose, sucrose, fructose) and sweeteners (xylitol, sorbitol) - with refractometric detection. The limits of detection of organic acids in liquid samples were 0.05-2.8 mg / l, in solid 0.7-3.1%. The detection limits for carbohydrates and sweeteners in liquid samples were 0.1-0.6 g/ l, in solid samples of 0.1-0.6 %. Samples or their solutions were purified from interfering organic impurities on solid phase extraction cartridges (SPE) C18, then were analyzed by HPLC.Key words: RP HPLC, spectrophotometric detection, refractometric detection, organic acids, carbohydrates and sweeteners, food, solid-phase extraction(Russian)DOI:Β http://dx.doi.org/10.15826/analitika.2013.17.2.011A.M. Zaharova*, L.A. Kartsova**, I.L. Greenstein**Company "Analyte", St. Petersburg,Β Russian Federation**St. Petersburg State University,Β St. Petersburg,Β Russian FederationΠΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΎΠ±ΡΠ°ΡΠ΅Π½Π½ΠΎ-ΡΠ°Π·ΠΎΠ²ΠΎΠΉ Π²ΡΡΠΎΠΊΠΎΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠ€ ΠΠΠΠ₯) Π²ΡΡΠ²Π»Π΅Π½ΠΎ ΡΠΎΠ΄Π΅ΡΠΆΠ°Π½ΠΈΠ΅ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ ΠΈ ΡΠ³Π»Π΅Π²ΠΎΠ΄ΠΎΠ² Π² ΠΏΡΠΎΠ±Π°Ρ
Β Π²ΠΈΠ½Π°, ΡΠΎΠΊΠ°, ΠΌΠΎΠ»ΠΎΡΠ½ΡΡ
ΠΏΡΠΎΠ΄ΡΠΊΡΠΎΠ², Π±ΠΈΠΎΠ»ΠΎΠ³ΠΈΡΠ΅ΡΠΊΠΈ Π°ΠΊΡΠΈΠ²Π½ΡΡ
Π΄ΠΎΠ±Π°Π²ΠΊΠ°Ρ
. ΠΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΊΠΈΡΠ»ΠΎΡΡ (ΡΠ°Π²Π΅Π»Π΅Π²Π°Ρ, Π²ΠΈΠ½Π½Π°Ρ, ΠΌΡΡΠ°Π²ΡΠΈΠ½Π°Ρ, ΡΠ±Π»ΠΎΡΠ½Π°Ρ, ΠΌΠΎΠ»ΠΎΡΠ½Π°Ρ, ΡΠΊΡΡΡΠ½Π°Ρ, Π»ΠΈΠΌΠΎΠ½Π½Π°Ρ, ΡΠ½ΡΠ°ΡΠ½Π°Ρ, ΡΡΠΌΠ°ΡΠΎΠ²Π°Ρ, ΠΏΡΠΎΠΏΠΈΠΎΠ½ΠΎΠ²Π°Ρ) ΠΎΠΏΡΠ΅Π΄Π΅Π»ΡΠ»ΠΈ Ρ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ ΡΠΏΠ΅ΠΊΡΡΠΎΡΠΎΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ; ΡΠ³Π»Π΅Π²ΠΎΠ΄Ρ (Π³Π»ΡΠΊΠΎΠ·Π°, Π»Π°ΠΊΡΠΎΠ·Π°, ΠΌΠ°Π»ΡΡΠΎΠ·Π°, ΠΌΠ°Π½Π½ΠΎΠ·Π°, ΡΠ°Ρ
Π°ΡΠΎΠ·Π°, ΡΡΡΠΊΡΠΎΠ·Π°) ΠΈ ΠΏΠΎΠ΄ΡΠ»Π°ΡΡΠΈΡΠ΅Π»ΠΈ (ΠΊΡΠΈΠ»ΠΈΡΠΎΠ», ΡΠΎΡΠ±ΠΈΡΠΎΠ») - Ρ ΡΠ΅ΡΡΠ°ΠΊΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠΌ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ. ΠΡΠ΅Π΄Π΅Π»Ρ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ Π² ΠΆΠΈΠ΄ΠΊΠΈΡ
ΠΏΡΠΎΠ±Π°Ρ
ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ 0.05-2.8 ΠΌΠ³/Π»; Π² ΡΠ²ΡΡΠ΄ΡΡ
- 4.10-5-2.10-3 % ΠΌΠ°Ρ. ΠΡΠ΅Π΄Π΅Π»Ρ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ ΡΠ³Π»Π΅Π²ΠΎΠ΄ΠΎΠ² ΠΈ ΠΏΠΎΠ΄ΡΠ»Π°ΡΡΠΈΡΠ΅Π»Π΅ΠΉ Π² ΠΆΠΈΠ΄ΠΊΠΈΡ
ΠΏΡΠΎΠ±Π°Ρ
- 0.1-0.6 Π³/Π», Π² ΡΠ²Π΅ΡΠ΄ΡΡ
- 0.1-0.6 % ΠΌΠ°Ρ. ΠΠ½Π°Π»ΠΈΠ·ΠΈΡΡΠ΅ΠΌΡΠ΅ ΠΏΡΠΎΠ±Ρ ΠΈΠ»ΠΈ ΠΈΡ
ΡΠ°ΡΡΠ²ΠΎΡΡΒ ΠΎΡΠΈΡΠ°Π»ΠΈ ΠΎΡ ΠΌΠ΅ΡΠ°ΡΡΠΈΡ
ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
ΠΏΡΠΈΠΌΠ΅ΡΠ΅ΠΉ Π½Π° ΠΊΠ°ΡΡΡΠΈΠ΄ΠΆΠ°Ρ
Β Π΄Π»Ρ ΡΠ²Π΅ΡΠ΄ΠΎΡΠ°Π·Π½ΠΎΠΉ ΡΠΊΡΡΡΠ°ΠΊΡΠΈΠΈ (Π’Π€Π).ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°:ΠΠ€ ΠΠΠΠ₯, ΡΠΏΠ΅ΠΊΡΡΠΎΡΠΎΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΎΠ΅ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅, ΡΠ΅ΡΡΠ°ΠΊΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΎΠ΅ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅, ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΊΠΈΡΠ»ΠΎΡΡ, ΡΠ³Π»Π΅Π²ΠΎΠ΄Ρ ΠΈ ΠΏΠΎΠ΄ΡΠ»Π°ΡΡΠΈΡΠ΅Π»ΠΈ, ΠΏΠΈΡΠ΅Π²ΡΠ΅ ΠΏΡΠΎΠ΄ΡΠΊΡΡ, ΡΠ²Π΅ΡΠ΄ΠΎΡΠ°Π·Π½Π°Ρ ΡΠΊΡΡΡΠ°ΠΊΡΠΈΡ.DOI:Β http://dx.doi.org/10.15826/analitika.2013.17.2.01
Chromatographic and liquid chromatography-tandem-mass spectrometry determination of first-line anti-tuberculosis drugs in human plasma
Π ΡΠ°Π±ΠΎΡΠ΅ Π²ΡΡΠ²Π»Π΅Π½Ρ Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΠΈ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΠ΅ΡΡΡΠ΅Ρ
ΠΏΡΠΎΡΠΈΠ²ΠΎΡΡΠ±Π΅ΡΠΊΡΠ»Π΅Π·Π½ΡΡ
ΠΏΡΠ΅ΠΏΠ°ΡΠ°ΡΠΎΠ² (ΠΠ’Π) ( ΡΡΠ°ΠΌΠ±ΡΡΠΎΠ», ΠΏΠΈΡΠ°Π·ΠΈΠ½Π°ΠΌΠΈΠ΄, ΠΈΠ·ΠΎΠ½ΠΈΠ°Π·ΠΈΠ΄, ΡΠΈΡΠ°ΠΌΠΏΠΈΡΠΈΠ½ ) ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΎΠ±ΡΠ°ΡΡΠ½Π½ΠΎ-ΡΠ°Π·ΠΎΠ²ΠΎΠΉ ΠΠΠΠ₯ (ΠΠ€ ΠΠΠΠ₯) ΠΈ ΠΈΠΎΠ½-ΠΏΠ°ΡΠ½ΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ Π²Π°ΡΠΈΠ°Π½Ρ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΡΠΈΡ
ΠΠ’Π Π² ΠΏΠ»Π°Π·ΠΌΠ΅ ΠΊΡΠΎΠ²ΠΈ ΡΠ΅Π»ΠΎΠ²Π΅ΠΊΠ° ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΠ€ ΠΠΠΠ₯ Ρ ΡΠ°Π½Π΄Π΅ΠΌΠ½ΡΠΌ ΠΌΠ°ΡΡ-ΡΠΏΠ΅ΠΊΡΡΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠΌ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Ρ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΏΡΠ΅ΠΉ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΠ΅ΠΉ. ΠΠ΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΎΡΡΡΠ΅ΡΡΠ²Π»ΡΠ»ΠΈ Π² ΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΏΠΎΠ»ΠΎΠΆΠΈΡΠ΅Π»ΡΠ½ΠΎΠΉ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΠΈ ΠΏΡΡΡΠΌ ΠΌΠΎΠ½ΠΈΡΠΎΡΠΈΠ½Π³Π° ΠΌΠ½ΠΎΠΆΠ΅ΡΡΠ²Π΅Π½Π½ΡΡ
ΡΠ΅Π°ΠΊΡΠΈΠΉ (MRM). ΠΠΏΡΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ ΡΡΠ°Π³ΠΌΠ΅Π½ΡΠ°ΡΠΈΠΈ Π΄Π»Ρ ΠΊΠ°ΠΆΠ΄ΠΎΠ³ΠΎ Π»Π΅ΠΊΠ°ΡΡΡΠ²Π΅Π½Π½ΠΎΠ³ΠΎ Π²Π΅ΡΠ΅ΡΡΠ²Π°. ΠΠ°ΠΉΠ΄Π΅Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ ΠΏΠΎΠ΄Π³ΠΎΡΠΎΠ²ΠΊΠΈ ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ ΠΊ ΠΠΠΠ₯/ΠΠ‘ Π°Π½Π°Π»ΠΈΠ·Ρ, Π²ΠΊΠ»ΡΡΠ°ΡΡΠΈΠ΅ ΠΎΡΠ°ΠΆΠ΄Π΅Π½ΠΈΠ΅ Π±Π΅Π»ΠΊΠΎΠ² ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ Π°ΡΠ΅ΡΠΎΠ½ΠΈΡΡΠΈΠ»ΠΎΠΌ. ΠΠ½Π°ΡΠ΅Π½ΠΈΡ ΡΡΠ΅ΠΏΠ΅Π½Π΅ΠΉ ΠΈΠ·Π²Π»Π΅ΡΠ΅Π½ΠΈΡ ΠΠ’Π ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ 85-90 %. ΠΡΠΎΠ²Π΅Π΄Π΅Π½Π° ΠΎΡΠ΅Π½ΠΊΠ° Π²Π»ΠΈΡΠ½ΠΈΡ ΠΌΠ°ΡΡΠΈΡΡ ΠΏΡΠΎΠ±Ρ Π½Π° ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠ΅ ΠΈ ΠΈΠΎΠ½ΠΈΠ·Π°ΡΠΈΡ ΠΠ’Π ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΏΠΎΡΡ-ΡΠΊΡΡΡΠ°ΠΊΡΠΈΠΎΠ½Π½ΠΎΠΉ Π΄ΠΎΠ±Π°Π²ΠΊΠΈ. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΡΠ°Π·Π±Π°Π²Π»Π΅Π½ΠΈΠ΅ ΡΠΊΡΡΡΠ°ΠΊΡΠ° ΠΏΠ»Π°Π·ΠΌΡ ΠΊΡΠΎΠ²ΠΈ Π² 10 ΡΠ°Π· Π΄ΠΎΡΡΠ°ΡΠΎΡΠ½ΠΎ Π΄Π»Ρ ΡΡΠ΅Π±ΡΠ΅ΠΌΠΎΠ³ΠΎ ΡΠ½ΠΈΠΆΠ΅Π½ΠΈΡ ΠΌΠ°ΡΡΠΈΡΠ½ΠΎΠ³ΠΎ ΡΡΡΠ΅ΠΊΡΠ°. ΠΠ·ΡΡΠ΅Π½Π° ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΡ ΠΠ’Π Π² ΠΏΡΠΎΡΠ΅ΡΡΠ΅ Π°Π½Π°Π»ΠΈΠ·Π° (Π°Π²ΡΠΎΡΠ°ΠΌΠΏΠ»Π΅Ρ 1 ΠΈ 12 Ρ.) ΠΈ Π² ΡΡΠ»ΠΎΠ²ΠΈΡΡ
Ρ
ΡΠ°Π½Π΅Π½ΠΈΡ (3 ΡΠΈΠΊΠ»Π° Π·Π°ΠΌΠΎΡΠΎΠ·ΠΊΠ°-ΡΠ°Π·ΠΌΠΎΡΠΎΠ·ΠΊΠ°). ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ ΡΠΏΠΎΡΠΎΠ± ΡΠ²Π΅Π»ΠΈΡΠ΅Π½ΠΈΡ ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΠΈ ΡΠΈΡΠ°ΠΌΠΏΠΈΡΠΈΠ½Π° Ρ Π΄ΠΎΠ±Π°Π²Π»Π΅Π½ΠΈΠ΅ΠΌ Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ Π°Π½ΡΠΈΠΎΠΊΡΠΈΠ΄Π°Π½ΡΠ° Π°ΡΠΊΠΎΡΠ±ΠΈΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ (1 ΠΌΠ³/ΠΌΠ»). ΠΡΠ΅Π΄Π΅Π»Ρ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ Ρ Π£Π€ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ ΠΎΡ 2 Π΄ΠΎ 20 ΠΌΠΊΠ³/ΠΌΠ», Ρ ΠΠ‘ Π΄Π΅ΡΠ΅ΠΊΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Π² SIM-ΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΎΡ 2 Π΄ΠΎ 15 Π½Π³/ΠΌΠ» ΠΈ Π² MRM-ΡΠ΅ΠΆΠΈΠΌΠ΅ ΠΎΡ 0.5 Π΄ΠΎ 10 Π½Π³/ΠΌΠ». Π ΠΎΠΏΡΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Π½ΡΡ
ΡΡΠ»ΠΎΠ²ΠΈΡΡ
ΠΏΠΎΠΊΠ°Π·Π°Π½Π° Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΡ ΠΎΠ±Π½Π°ΡΡΠΆΠ΅Π½ΠΈΡ ΠΈ ΠΊΠΎΠ»ΠΈΡΠ΅ΡΡΠ²Π΅Π½Π½ΠΎΠ³ΠΎ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΡ Π²ΡΠ΅Ρ
ΡΠ΅ΡΡΡΠ΅Ρ
ΠΠ’Π Π² ΠΏΠ»Π°Π·ΠΌΠ΅ ΠΊΡΠΎΠ²ΠΈ Π±ΠΎΠ»ΡΠ½ΠΎΠ³ΠΎ ΡΡΠ±Π΅ΡΠΊΡΠ»Π΅Π·ΠΎΠΌ Ρ ΠΏΡΠΎΠ²ΠΎΠ΄ΠΈΠΌΠΎΠΉ Π»Π΅ΠΊΠ°ΡΡΡΠ²Π΅Π½Π½ΠΎΠΉ ΡΠ΅ΡΠ°ΠΏΠΈΠ΅ΠΉ.In the current study the possibility of the simultaneous determination of anti-tuberculosis (anti-TB) drugs (isoniazid, pyrazinamide, ethambutol and rifampicin) using the reversed-phase HPLC (RP-HPLC) and ion-pair chromatography was investigated. A selective and highly sensitive liquid chromatography/tandem mass spectrometry method for the simultaneous determination of four anti-TB drugs (isoniazid, pyrazinamide, ethambutol and rifampicin) in the human plasma was developed. The detection was carried out using the multiple reaction-monitoring (MRM) modes with positive polarity. The fragmentation conditions for each drug were optimized, and the conditions for the blood plasma preparation for HPLC/MS analysis, including the protein precipitation with ACN with a ratio of 3:1 (by volume), were chosen. The matrix effects on the separation and ionization of anti-TB drugs were estimated by the post-extraction additives method. It was shown that the 10-fold dilution of plasma extracts was sufficient to decrease the influence of the sample matrix. The stability of anti-TB drugs during the analysis (in autosampler at 1 and 12 hours) and at storage conditions (3 cycles of freeze-thaw) was studied. The method for increasing the stability of rifampicin using ascorbic acid (1 mg/ml) as antioxidant was provided. The LOD with UV detection were 2 - 20 Β΅g/ml, in SIM-mode - 2 - 15 ng/ml and in MRM-mode - 0.5 - 10 ng/ml respectively. The possibility of the determination of four anti-TB drugs in real plasma samples of patients with tuberculosis undergoing drug therapy in optimized conditions HPLC/MC was shown
ΠΠ ΠΠΠΠΠΠΠΠ ΠΠ«Π‘ΠΠΠΠΠ‘ΠΠΠΠΠΠΠ ΠΠΠΠΠΠΠΠΠ’Π Π ΠΠΠΠΠΠΠ―Π ΠΠΠ ΠΠΠΠΠ’Π ΠΠ€ΠΠ ΠΠΠ ΠΠΠ― Π ΠΠΠΠΠΠΠΠΠ― Π ΠΠΠΠ¦ΠΠΠ’Π ΠΠ ΠΠΠΠΠΠ― ΠΠΠΠ ΠΠΠΠΠ§ΠΠ‘ΠΠΠ₯ ΠΠΠΠΠΠΠ
In this study, the possibilities of using the highly basic nano-sized anionite based on the anionite AB-17 as a modifier of the background electrolyte (BGE) in the capillary electrophoresis (CE) for the separation of inorganic anions was investigated. The influence of the concentration of nano-sized anionite in BGE on the velocity and direction of EOF as well as on the efficiency (N, t.p./m) and peaks resolution (R) of inorganic anions was determined. It was established that the addition of the highly basic nano-sized anionite to the BGE (with the concentration of functional groups of nano-sized anionite more than 0.1 mM) leads to the reversal of the EOF. This indicates the dynamic modification of the silica capillary walls by the particles of nano-sized anionites and leads to the better efficiency (up to 1Β 200* 103 t.p./m) and increased resolution of inorganic anions compared to BGE containing conventional cationic surfactant β CTAB.Β Various on-line concentration technics were applied to decrease the LOD of analytes. The LOD of inorganic anions with UV detection and nano-sized anionite as a modifier of BGE were 8-30 ng/ml in case of field amplified sample stacking and 1pg/ml β 7ΞΌg/ml for the electro stacking respectively. Thus, the new method of simultaneous electrophoretic determination of 8 inorganic anions was developed and realized for the quantitative analysis of inorganic anions in urine.Key words: capillary electrophoresis, inorganic anions, strong basic nano-sized anionite, on-lineconcentration(Russian)DOI: http://dx.doi.org/10.15826/analitika.2017.21.1.004Dzema D.V., Kartsova L.A., Polikarpova D.A.Saint-Petersburg State University, Institute of Chemistry7/9 Universitetskaya nab., St. Petersburg, 199034, Russian FederatinΒ Π Π°Π±ΠΎΡΠ° ΠΏΠΎΡΠ²ΡΡΠ΅Π½Π° Π²ΡΡΠ²Π»Π΅Π½ΠΈΡ Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΠ΅ΠΉ Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡΠ°Β Π½Π° ΠΎΡΠ½ΠΎΠ²Π΅ Π²ΡΡΠΎΠΊΠΎΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ³ΠΎ Π°Π½ΠΈΠΎΠ½ΠΈΡΠ° ΠΠ-17 Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΠΌΠΎΠ΄ΠΈΡΠΈΠΊΠ°ΡΠΎΡΠ° ΡΠΎΠ½ΠΎΠ²ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΠ° Π² ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠΌ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅Π·Π΅ (ΠΠ) Π΄Π»Ρ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΠ³ΠΎ ΠΈ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΠ³ΠΎ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡΒ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ². ΠΡΡΠ²Π»Π΅Π½ΠΎ Π²Π»ΠΈΡΠ½ΠΈΠ΅ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΠΈ Π½Π°Π½ΠΎΠΈΠΎΠ½ΠΈΡΠ° Π² ΡΠΎΡΡΠ°Π²Π΅ ΡΠΎΠ½ΠΎΠ²ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΠ° Π½Π° Π²Π΅Π»ΠΈΡΠΈΠ½Ρ ΠΈ Π·Π½Π°ΠΊ ΡΠ»Π΅ΠΊΡΡΠΎΠΎΡΠΌΠΎΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΠΎΡΠΎΠΊΠ° (ΠΠΠ), Π° ΡΠ°ΠΊΠΆΠ΅ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡ ΠΈ ΡΠ°ΠΊΡΠΎΡΡ ΡΠ°Π·ΡΠ΅ΡΠ΅Π½ΠΈΡ Β ΠΏΡΠΈ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠΈ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ². ΠΠΏΠ΅ΡΠ²ΡΠ΅ ΡΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π΄ΠΎΠ±Π°Π²ΠΊΠ° Π²ΡΡΠΎΠΊΠΎΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ³ΠΎ Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡΠ° Π² ΡΠΎΠ½ΠΎΠ²ΡΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΒ Π² ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΠΈ, ΠΏΡΠ΅Π²ΡΡΠ°ΡΡΠ΅ΠΉ 0.1 ΠΌΠ ΠΏΠΎ ΡΡΠ½ΠΊΡΠΈΠΎΠ½Π°Π»ΡΠ½ΡΠΌ Π³ΡΡΠΏΠΏΠ°ΠΌ, ΠΏΡΠΈΠ²ΠΎΠ΄ΠΈΡ ΠΊ ΠΎΠ±ΡΠ°ΡΠ΅Π½ΠΈΡ ΡΠ»Π΅ΠΊΡΡΠΎΠΎΡΠΌΠΎΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΠΎΡΠΎΠΊΠ°. ΠΡΠΎ ΡΠ²ΠΈΠ΄Π΅ΡΠ΅Π»ΡΡΡΠ²ΡΠ΅Ρ ΠΎ Π΄ΠΈΠ½Π°ΠΌΠΈΡΠ΅ΡΠΊΠΎΠΉ ΠΌΠΎΠ΄ΠΈΡΠΈΠΊΠ°ΡΠΈΠΈ ΡΡΠ΅Π½ΠΎΠΊ ΠΊΠ²Π°ΡΡΠ΅Π²ΠΎΠ³ΠΎ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° ΠΈ ΠΏΡΠΈΠ²ΠΎΠ΄ΠΈΡ ΠΊ ΡΠΎΡΡΡ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΠΈ Β ΠΈ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΠΈ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ² ΠΏΠΎ ΡΡΠ°Π²Π½Π΅Π½ΠΈΡ Ρ ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΠ°ΠΌΠΈ, ΠΏΠΎΠ»ΡΡΠ°Π΅ΠΌΡΠΌΠΈ Ρ ΡΡΠ°Π΄ΠΈΡΠΈΠΎΠ½Π½ΡΠΌ ΠΊΠ°ΡΠΈΠΎΠ½Π½ΡΠΌ Π΄Π΅ΡΠ΅ΡΠ³Π΅Π½ΡΠΎΠΌ ΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΌΠ΅ΡΠΈΠ»Π°ΠΌΠΌΠΎΠ½ΠΈΠΉ Π±ΡΠΎΠΌΠΈΠ΄ΠΎΠΌ (Π¦Π’ΠΠ). ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½ Π²Π°ΡΠΈΠ°Π½ΡΒ ΠΎΠ΄Π½ΠΎΠ²ΡΠ΅ΠΌΠ΅Π½Π½ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ Π²ΠΎΡΡΠΌΠΈ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ² Ρ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠ΅ΠΌ Π²ΡΡΠΎΠΊΠΎΠΎΡΠ½ΠΎΠ²Π½ΠΎΠ³ΠΎ Π°Π½ΠΈΠΎΠ½ΠΈΡΠ°. ΠΡΡΠ²Π»Π΅Π½Ρ Π²ΠΎΠ·ΠΌΠΎΠΆΠ½ΠΎΡΡΠΈ ΡΠ°Π·Π»ΠΈΡΠ½ΡΡ
Π²Π°ΡΠΈΠ°Π½ΡΠΎΠ² Π²Π½ΡΡΡΠΈΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠ³ΠΎ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠΈΡΠΎΠ²Π°Π½ΠΈΡ: ΡΡΡΠΊΠΈΠ½Π³Π° Ρ ΡΡΠΈΠ»Π΅Π½ΠΈΠ΅ΠΌ ΠΏΠΎΠ»Ρ ΠΈ ΡΠ»Π΅ΠΊΡΡΠΎΡΡΡΠΊΠΈΠ½Π³Π°. Π Π°Π·ΡΠ°Π±ΠΎΡΠ°Π½Π½ΡΠΉ Π²Π°ΡΠΈΠ°Π½Ρ ΡΠ΅Π°Π»ΠΈΠ·ΠΎΠ²Π°Π½ ΠΏΡΠΈ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠΈ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ² Π² ΠΌΠΎΡΠ΅.ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΡΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅Π·, Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΠ΅ Π°Π½ΠΈΠΎΠ½Ρ, Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡ, on-lineΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅DOI: http://dx.doi.org/10.15826/analitika.2017.21.1.00
ΠΠΠΠΠ ΠΠΠΠΠ ΠΠ«Π ΠΠΠΠΠ’Π« β Π‘Π’ΠΠ¦ΠΠΠΠΠ ΠΠ«Π Π€ΠΠΠ« ΠΠΠ― ΠΠΠΠΠΠΠ―Π ΠΠΠ ΠΠΠΠΠ’Π ΠΠ₯Π ΠΠΠΠ’ΠΠΠ ΠΠ€ΠΠ
Nano-sized ion exchangers possess high ion exchange capacity, adhesion to quartz surface and pH-independent charge, which make them promising modifiers of the stationary phases for the high-efficient and selective separation of charged analytes in the capillary electrochromatography mode. The goal of the investigation was the application of nano-sized ion exchangers as stationary phases in the capillary electrochromatography. The development of coatings based on nano-sized anion and cation exchangers (polystyrene-divinylbenzene copolymer matrix functionalized with quaternary ammonium and sulfo groups respectively) was proposed for the first time. The proposed procedures of coatings formation were very fast (less than 15 min) and were reproducible. The characterization of coatings was also carried out by the scanning electron microscopy. The high stability of the nano-sized anion exchange coating allowed using background electrolytes with pH range from 2 to 10 for the electrophoretic separations. The lower stability of coatings based on nano-sized cation exchange particles of fused silica capillaries reduced the pH range of possible background electrolytes (pH 2 - 8). Modified by nano-sized anion exchangers capillaries were applied for the separation of inorganic anions and organic acids. The determination of these analytes was characterized by high efficiency, resolution (compared to the results obtained without nano-sized anion exchanger) and short analysis time due to the co-directional migration of analytes and reversed electroosmotic flow. The modification of the fused silica capillary by nano-sized cation exchange particles prevented the sorption of biogenic amines during their electrophoretic separation.Keywords: capillary electrochromatography, nano-sized anion-exchanger, nano-sized cation-exchanger, coatings of fused-silica capillary wallsDOI: http://dx.doi.org/10.15826/analitika.2018.22.3.006(Russian)D.V. Makeeva, L.A. Kartsova, D.A. PolikarpovaΒ Saint-Petersburg State University, Institute of Chemistry, 7/9 Universitetskaya nab.,Β St. Petersburg, 199034, Russian FederationΠΡΡΠΎΠΊΠ°Ρ ΠΈΠΎΠ½ΠΎΠΎΠ±ΠΌΠ΅Π½Π½Π°Ρ Π΅ΠΌΠΊΠΎΡΡΡ, Π°Π΄Π³Π΅Π·ΠΈΡ ΠΊ ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ ΠΊΠ²Π°ΡΡΠ° ΠΈ Π½Π΅Π·Π°Π²ΠΈΡΠΈΠΌΡΠΉ ΠΎΡ ΡΠ Π·Π°ΡΡΠ΄ ΠΏΠΎΠ·Π²ΠΎΠ»ΡΡΡ ΡΠ°ΡΡΠΌΠ°ΡΡΠΈΠ²Π°ΡΡ Π½Π°Π½ΠΎΠΈΠΎΠ½ΠΈΡΡ Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΠΏΠ΅ΡΡΠΏΠ΅ΠΊΡΠΈΠ²Π½ΡΡ
ΠΌΠΎΠ΄ΠΈΡΠΈΠΊΠ°ΡΠΎΡΠΎΠ² ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΈΡ
ΡΠΈΡΡΠ΅ΠΌ, ΡΠΏΠΎΡΠΎΠ±ΡΡΠ²ΡΡΡΠΈΡ
Π²ΡΡΠΎΠΊΠΎΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΠΌΡ ΠΈ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΠΌΡ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ Π°Π½Π°Π»ΠΈΡΠΎΠ². ΠΠ°Π½Π½Π°Ρ ΡΠ°Π±ΠΎΡΠ° ΠΏΠΎΡΠ²ΡΡΠ΅Π½Π° ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ΠΈΡ Π½Π°Π½ΠΎΡΠ°Π·ΠΌΠ΅ΡΠ½ΡΡ
ΠΈΠΎΠ½ΠΈΡΠΎΠ² Π² ΠΊΠ°ΡΠ΅ΡΡΠ²Π΅ ΡΡΠ°ΡΠΈΠΎΠ½Π°ΡΠ½ΡΡ
ΡΠ°Π· Π΄Π»Ρ ΡΠ΅Π°Π»ΠΈΠ·Π°ΡΠΈΠΈ ΡΠ΅ΠΆΠΈΠΌΠ° ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½ΠΎΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠΠ₯). Π ΡΠ°ΠΌΠΊΠ°Ρ
ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΈΡ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½Ρ ΡΡΠ»ΠΎΠ²ΠΈΡ ΡΠΎΡΠΌΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΠΏΠΎΠΊΡΡΡΠΈΠΉ ΡΡΠ΅Π½ΠΎΠΊ ΠΊΠ²Π°ΡΡΠ΅Π²ΠΎΠ³ΠΎ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° Π½Π° ΠΎΡΠ½ΠΎΠ²Π΅ Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡΠ° ΠΈ Π½Π°Π½ΠΎΠΊΠ°ΡΠΈΠΎΠ½ΠΈΡΠ° β ΡΠΎΠΏΠΎΠ»ΠΈΠΌΠ΅ΡΠΎΠ² ΡΡΠΈΡΠΎΠ»Π° ΠΈ Π΄ΠΈΠ²ΠΈΠ½ΠΈΠ»Π±Π΅Π½Π·ΠΎΠ»Π°, ΡΡΠ½ΠΊΡΠΈΠΎΠ½Π°Π»ΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Π½ΡΡ
ΡΠ΅ΡΠ²Π΅ΡΡΠΈΡΠ½ΡΠΌΠΈ Π°ΠΌΠΌΠΎΠ½ΠΈΠΉΠ½ΡΠΌΠΈ ΠΈ ΡΡΠ»ΡΡΠΎΠ³ΡΡΠΏΠΏΠ°ΠΌΠΈ, ΡΠΎΠΎΡΠ²Π΅ΡΡΡΠ²Π΅Π½Π½ΠΎ. ΠΡΠ΅Π΄Π»ΠΎΠΆΠ΅Π½Π½ΡΠ΅ ΠΏΠΎΠ΄Ρ
ΠΎΠ΄Ρ ΠΊ ΡΠΎΡΠΌΠΈΡΠΎΠ²Π°Π½ΠΈΡ ΡΡΠ°ΡΠΈΠΎΠ½Π°ΡΠ½ΡΡ
ΡΠ°Π· Π² ΠΊΠ²Π°ΡΡΠ΅Π²ΠΎΠΌ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ΅ ΠΎΡΠ»ΠΈΡΠ°ΡΡΡΡ Π²ΡΡΠΎΠΊΠΎΠΉ ΡΠΊΡΠΏΡΠ΅ΡΡΠ½ΠΎΡΡΡΡ (10-15 ΠΌΠΈΠ½ΡΡ) ΠΈ Π²ΡΡΠΎΠΊΠΎΠΉ Π²ΠΎΡΠΏΡΠΎΠΈΠ·Π²ΠΎΠ΄ΠΈΠΌΠΎΡΡΡΡ ΠΎΡ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° ΠΊ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΡ. ΠΠΎΠ»ΡΡΠ΅Π½Π½ΡΠ΅ ΠΏΠΎΠΊΡΡΡΠΈΡ Π±ΡΠ»ΠΈ ΠΎΡ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΠ·ΠΎΠ²Π°Π½Ρ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΡΠΊΠ°Π½ΠΈΡΡΡΡΠ΅ΠΉ ΡΠ»Π΅ΠΊΡΡΠΎΠ½Π½ΠΎΠΉ ΠΌΠΈΠΊΡΠΎΡΠΊΠΎΠΏΠΈΠΈ.Β ΠΡΡΠΎΠΊΠ°Ρ ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΡ ΠΏΠΎΠΊΡΡΡΠΈΡ Π½Π° ΠΎΡΠ½ΠΎΠ²Π΅ Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡΠ° ΠΏΠΎΠ·Π²ΠΎΠ»ΡΠ΅Ρ ΠΈΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°ΡΡ Π΄Π»Ρ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ ΡΠΎΠ½ΠΎΠ²ΡΠ΅ ΡΠ»Π΅ΠΊΡΡΠΎΠ»ΠΈΡΡ Ρ ΡΠ Π² Π΄ΠΈΠ°ΠΏΠ°Π·ΠΎΠ½Π΅ ΠΎΡ 2 Π΄ΠΎ 10 Π΅Π΄ΠΈΠ½ΠΈΡ; ΠΌΠ΅Π½ΡΡΠ°Ρ ΡΡΠ°Π±ΠΈΠ»ΡΠ½ΠΎΡΡΡ Π½Π°Π½ΠΎΠΊΠ°ΡΠΈΠΎΠ½ΠΈΡΠ° Π½Π° ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ ΠΊΠ²Π°ΡΡΠ΅Π²ΠΎΠ³ΠΎ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° ΡΠΎΠΊΡΠ°ΡΠ°Π΅Ρ ΡΠ°Π±ΠΎΡΠΈΠΉ Π΄ΠΈΠ°ΠΏΠ°Π·ΠΎΠ½ ΡΠ (2 β 8). ΠΠΎΠΊΠ°Π·Π°Π½Ρ ΠΏΠ΅ΡΡΠΏΠ΅ΠΊΡΠΈΠ²Ρ ΠΏΡΠΈΠΌΠ΅Π½Π΅Π½ΠΈΡ ΠΊΠ²Π°ΡΡΠ΅Π²ΡΡ
ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠΎΠ², ΠΌΠΎΠ΄ΠΈΡΠΈΡΠΈΡΠΎΠ²Π°Π½Π½ΡΡ
Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡΠΎΠΌ, ΠΏΡΠΈ ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΠΈ Π½Π΅ΠΎΡΠ³Π°Π½ΠΈΡΠ΅ΡΠΊΠΈΡ
Π°Π½ΠΈΠΎΠ½ΠΎΠ² ΠΈ ΠΊΠ°ΡΠ±ΠΎΠ½ΠΎΠ²ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ. Π Π°Π·Π΄Π΅Π»Π΅Π½ΠΈΠ΅ ΡΠΊΠ°Π·Π°Π½Π½ΡΡ
Π°Π½Π°Π»ΠΈΡΠΎΠ² Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΠ·ΡΠ΅ΡΡΡ Π²ΡΡΠΎΠΊΠΎΠΉ ΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡΡ, Π±ΠΎΠ»ΡΡΠ΅ΠΉ ΡΠ΅Π»Π΅ΠΊΡΠΈΠ²Π½ΠΎΡΡΡΡ ΡΠ°Π·Π΄Π΅Π»Π΅Π½ΠΈΡ, ΠΏΠΎ ΡΡΠ°Π²Π½Π΅Π½ΠΈΡ Ρ ΡΠ΅Π·ΡΠ»ΡΡΠ°ΡΠ°ΠΌΠΈ Π² ΠΎΡΡΡΡΡΡΠ²ΠΈΠ΅ ΠΌΠΎΠ΄ΠΈΡΠΈΠΊΠ°ΡΠΎΡΠ°, Π° ΡΠ°ΠΊΠΆΠ΅ ΡΠΊΡΠΏΡΠ΅ΡΡΠ½ΠΎΡΡΡΡ Π·Π° ΡΡΠ΅Ρ ΡΠΎΠ½Π°ΠΏΡΠ°Π²Π»Π΅Π½Π½ΠΎΠΉ ΠΌΠΈΠ³ΡΠ°ΡΠΈΠΈ Π°Π½Π°Π»ΠΈΡΠΎΠ² ΠΈ ΠΎΠ±ΡΠ°ΡΠ΅Π½Π½ΠΎΠ³ΠΎ ΡΠ»Π΅ΠΊΡΡΠΎΠΎΡΠΌΠΎΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΠΎΡΠΎΠΊΠ°. ΠΡΠΏΠΎΠ»ΡΠ·ΠΎΠ²Π°Π½ΠΈΠ΅ ΠΏΠΎΠΊΡΡΡΠΎΠ³ΠΎ ΡΠ°ΡΡΠΈΡΠ°ΠΌΠΈ Π½Π°Π½ΠΎΠΊΠ°ΡΠΈΠΎΠ½ΠΈΡΠ° ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ° ΠΏΠΎΠ·Π²ΠΎΠ»ΠΈΠ»ΠΎ ΠΏΡΠ΅Π΄ΠΎΡΠ²ΡΠ°ΡΠΈΡΡ ΡΠΎΡΠ±ΡΠΈΡ Π±ΠΈΠΎΠ³Π΅Π½Π½ΡΡ
Π°ΠΌΠΈΠ½ΠΎΠ² ΠΏΡΠΈ ΠΈΡ
ΡΠ»Π΅ΠΊΡΡΠΎΡΠΎΡΠ΅ΡΠΈΡΠ΅ΡΠΊΠΎΠΌ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½ΠΈΠΈ.ΠΠ»ΡΡΠ΅Π²ΡΠ΅ ΡΠ»ΠΎΠ²Π°: ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ½Π°Ρ ΡΠ»Π΅ΠΊΡΡΠΎΡ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡ, Π½Π°Π½ΠΎΠ°Π½ΠΈΠΎΠ½ΠΈΡ, Π½Π°Π½ΠΎΠΊΠ°ΡΠΈΠΎΠ½ΠΈΡ, ΠΏΠΎΠΊΡΡΡΠΈΡ ΡΡΠ΅Π½ΠΎΠΊ ΠΊΠ°ΠΏΠΈΠ»Π»ΡΡΠ°DOI: http://dx.doi.org/10.15826/analitika.2018.22.3.00
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