240 research outputs found
The cooperative effect of the third component on the isotherms of guest vapour inclusion in solid tert-butylcalix[4]arene
The observed sigmoidal isotherms of guest vapour sorption on solid tert-butylcalix[4]arene may be transformed to Langmuir or BET isotherms in the presence of small concentrations of a third component
ΠΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½Π½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ 5,17-Π±ΡΡ-(n-toΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°- Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ Π· Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ ΠΌΠ΅ΡΠΎΠ΄Π°ΠΌΠΈ ΠΎΡ Π²Π΅ΡΡ ΡΠ° ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎΠ³ΠΎ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ
The Host-Guest complexation of 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene with benzoic acids has been studied by reversed-phase high-performance liquid chromatography (RP HPLC) method (the mobile phase β MeCN/H2O, 86/14 v/v, the column support β LiChrosorb RP 18, UV detector, l = 254 nm). The study of the chromatographic behaviour of 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene and benzoic acids, as well as determination of their main chromatographic characteristics β the retention times tR and capacity factors kβ have been performed. On the basis of the data obtained the lipophilicity log P, as well as the binding constants and Gibbs free energies of the complexes of 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene with benzoic acids have been calculated. The binding constants and Gibbs free energies of the complexes of 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene with benzoic acids are in the range of 335-910 Π-1 or -14.38 β -16.85 kJ/mol, respectively. The influence of the benzoic acids lipophilicity log P and pKa values on the binding constants KA of the complexes has been examined. It has been found that decrease of the log P and pKa values increases the binding constants KA of the complexes. Molecular modeling of the complexes revealed the presence of hydrogen bonds between carboxylic groups of the acids and nitrogen atoms of imino-groups at the upper rim or oxygen atoms of the hydroxyl groups at the lower rim of the calixarene macrocycle. A linear dependence of the binding constants from the acid lipophilicity log P indicates a significant role of solvatophobic interactions during the complexation process.ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠ΅ ΡΠΈΠΏΠ° ΠΠΎΡΡΡ-Π₯ΠΎΠ·ΡΠΈΠ½ 5,17-Π±ΠΈΡ-(N-ΡΠΎΠ»ΠΈΠ»ΠΈΠΌΠΈΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΠΈΠΊΡ[4]Π°ΡΠ΅Π½Π° Ρ Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΎ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΎΠ±ΡΠ°ΡΠ΅Π½Π½ΠΎΡΠ°Π·Π½ΠΎΠΉ Π²ΡΡΠΎΠΊΠΎΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠ€ ΠΠΠΠ₯) (ΠΏΠΎΠ΄Π²ΠΈΠΆΠ½Π°Ρ ΡΠ°Π·Π° β MeCN/H2O, 86/14, ΠΊΠΎΠ»ΠΎΠ½ΠΎΡΠ½Π°Ρ Π½Π°ΡΠ°Π΄ΠΊΠ° ΠΌΠ°ΡΠΊΠΈ LiChrosorb RP 18, Π£Π€-Π΄Π΅ΡΠ΅ΠΊΡΠΎΡ, l = 254 Π½ΠΌ). ΠΡΠΎΠ²Π΅Π΄Π΅Π½ΠΎ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΈΠ΅ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΏΠΎΠ²Π΅Π΄Π΅Π½ΠΈΡ ΠΈ ΠΎΠΏΡΠ΅Π΄Π΅Π»Π΅Π½Ρ ΠΎΡΠ½ΠΎΠ²Π½ΡΠ΅ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠΈ 5,17-Π±ΠΈΡ-(N-ΡΠΎΠ»ΠΈΠ»ΠΈΠΌΠΈΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΠΈΠΊΡ[4]Π°ΡΠ΅Π½Π°-ΡΠ΅ΡΠ΅ΠΏΡΠΎΡΠ° ΠΈ Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ-ΡΡΠ±ΡΡΡΠ°ΡΠΎΠ² β Π²ΡΠ΅ΠΌΠ΅Π½Π° ΡΠ΄Π΅ΡΠΆΠΈΠ²Π°Π½ΠΈΡ tR ΠΈ ΠΊΠΎΡΡΡΠΈΡΠΈΠ΅Π½ΡΡ Π΅ΠΌΠΊΠΎΡΡΠΈ kβ. ΠΠ° ΠΎΡΠ½ΠΎΠ²Π΅ ΠΏΠΎΠ»ΡΡΠ΅Π½Π½ΡΡ
Π΄Π°Π½Π½ΡΡ
ΡΠ°ΡΡΡΠΈΡΠ°Π½Ρ Π·Π½Π°ΡΠ΅Π½ΠΈΡ Π»ΠΈΠΏΠΎΡΠΈΠ»ΡΠ½ΠΎΡΡΠΈ log P Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ, Π° ΡΠ°ΠΊΠΆΠ΅ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ ΠΈ ΡΠ²ΠΎΠ±ΠΎΠ΄Π½ΡΡ
ΡΠ½Π΅ΡΠ³ΠΈΠΉ ΠΠΈΠ±Π±ΡΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² 5,17-Π±ΠΈΡ-(N-ΡΠΎΠ»ΠΈΠ»ΠΈΠΌΠΈΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΠΈΠΊΡ[4]Π°ΡΠ΅Π½Π° Ρ Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ. Π Π°ΡΡΡΠΈΡΠ°Π½Π½ΡΠ΅ Π·Π½Π°ΡΠ΅Π½ΠΈΡ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ ΠΈ ΡΠ²ΠΎΠ±ΠΎΠ΄Π½ΡΡ
ΡΠ½Π΅ΡΠ³ΠΈΠΉ ΠΠΈΠ±Π±ΡΠ° Π½Π°Ρ
ΠΎΠ΄ΡΡΡΡ Π² ΠΏΡΠ΅Π΄Π΅Π»Π°Ρ
335-910 Π-1 ΠΈ -14.38 β -16.85 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ, ΡΠΎΠΎΡΠ²Π΅ΡΡΡΠ²Π΅Π½Π½ΠΎ. ΠΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΎ Π²Π»ΠΈΡΠ½ΠΈΠ΅ Π»ΠΈΠΏΠΎΡΠΈΠ»ΡΠ½ΠΎΡΡΠΈ log P ΠΈ ΡΠΠ° Π·Π°ΠΌΠ΅ΡΠ΅Π½Π½ΡΡ
Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ Π½Π° ΠΊΠΎΠ½ΡΡΠ°Π½ΡΡ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ KA ΠΈΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² Ρ ΠΊΠ°Π»ΠΈΠΊΡaΡΠ΅Π½ΠΎΠΌ. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ ΠΊΠΎΠ½ΡΡΠ°Π½ΡΡ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ KA Π²ΠΎΠ·ΡΠ°ΡΡΠ°ΡΡ ΠΏΠΎ ΠΌΠ΅ΡΠ΅ ΡΠ½ΠΈΠΆΠ΅Π½ΠΈΡ Π·Π½Π°ΡΠ΅Π½ΠΈΠΉ Π»ΠΈΠΏΠΎΡΠΈΠ»ΡΠ½ΠΎΡΡΠΈ log P ΠΈ ΡΠΠ° Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ. ΠΡΠΎΠ²Π΅Π΄Π΅Π½Π½ΠΎΠ΅ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎΠ΅ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² ΠΏΠΎΠΊΠ°Π·Π°Π»ΠΎ Π½Π°Π»ΠΈΡΠΈΠ΅ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π½ΡΡ
ΡΠ²ΡΠ·Π΅ΠΉ ΠΌΠ΅ΠΆΠ΄Ρ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΡΠΌΠΈ Π³ΡΡΠΏΠΏΠ°ΠΌΠΈ Π±Π΅Π½Π·ΠΎΠΉΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ ΠΈ Π°ΡΠΎΠΌΠ°ΠΌΠΈ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π° ΠΈΠΌΠΈΠ½ΠΎΠ³ΡΡΠΏΠΏ Π²Π΅ΡΡ
Π½Π΅Π³ΠΎ ΠΎΠ±ΠΎΠ΄Π° ΠΈΠ»ΠΈ Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄Π° Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠ»ΡΠ½ΡΡ
Π³ΡΡΠΏΠΏ Π½ΠΈΠΆΠ½Π΅Π³ΠΎ ΠΎΠ±ΠΎΠ΄Π° ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½ΠΎΠ²ΠΎΠ³ΠΎ ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»Π°. ΠΠΈΠ½Π΅ΠΉΠ½Π°Ρ Π·Π°Π²ΠΈΡΠΈΠΌΠΎΡΡΡ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ ΠΎΡ Π»ΠΈΠΏΠΎΡΠΈΠ»ΡΠ½ΠΎΡΡΠΈ log P ΠΊΠΈΡΠ»ΠΎΡ ΡΠΊΠ°Π·ΡΠ²Π°Π΅Ρ Π½Π° Π·Π°ΠΌΠ΅ΡΠ½ΡΡ ΡΠΎΠ»Ρ ΡΠΎΠ»ΡΠ²Π°ΡΠΎΡΠΎΠ±Π½ΡΡ
Π²Π·Π°ΠΈΠΌΠΎΠ΄Π΅ΠΉΡΡΠ²ΠΈΠΉ ΠΏΡΠΈ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠΈ Ρ 5,17-Π±ΠΈΡ-(N-ΡΠΎΠ»ΠΈΠ»ΠΈΠΌΠΈΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΠΈΠΊΡ[4]Π°ΡΠ΅Π½ΠΎΠΌ.ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ ΡΠΈΠΏΡ ΠΡΡΡΡ-ΠΠΎΡΠΏΠΎΠ΄Π°Ρ 5,17-Π±ΡΡ-(N-ΡΠΎΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ Π· Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΠΎ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΎΠ±Π΅ΡΠ½Π΅Π½ΠΎ-ΡΠ°Π·Π½ΠΎΡ Π²ΠΈΡΠΎΠΊΠΎΠ΅ΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡ ΡΡΠ΄ΠΈΠ½Π½ΠΎΡ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡ (ΠΠ€ ΠΠΠ Π₯) (ΡΡΡ
ΠΎΠΌΠ° ΡΠ°Π·Π° - MeCN/H2O, 86/14 Π·Π° ΠΎΠ±βΡΠΌΠΎΠΌ, ΠΊΠΎΠ»ΠΎΠ½ΠΎΡΠ½Π° Π½Π°ΡΠ°Π΄ΠΊΠ° ΠΌΠ°ΡΠΊΠΈ LiChrosorb RP 18, Π£Π€-Π΄Π΅ΡΠ΅ΠΊΡΠΎΡ, l = 254 Π½ΠΌ). ΠΡΠΎΠ²Π΅Π΄Π΅Π½ΠΎ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½Π½Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡΠ½ΠΎΡ ΠΏΠΎΠ²Π΅Π΄ΡΠ½ΠΊΠΈ ΡΠ° Π²ΠΈΠ·Π½Π°ΡΠ΅Π½Ρ ΠΎΡΠ½ΠΎΠ²Π½Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡΠ½Ρ Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠΈ 5,17-Π±ΡΡ-(N-ΡΠΎΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ ΡΠ° Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ-ΡΡΠ±ΡΡΡΠ°ΡΡΠ² β ΡΠ°Ρ ΡΡΡΠΈΠΌΠ°Π½Π½Ρ tR ΡΠ° ΠΊΠΎΠ΅ΡΡΡΡΡΠ½ΡΠΈ ΡΠΌΠΊΠΎΡΡΡ kβ. ΠΠ° ΠΏΡΠ΄ΡΡΠ°Π²Ρ ΠΎΡΡΠΈΠΌΠ°Π½ΠΈΡ
Π΄Π°Π½ΠΈΡ
ΡΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½ΠΎ Π·Π½Π°ΡΠ΅Π½Π½Ρ Π»ΡΠΏΠΎΡΡΠ»ΡΠ½ΠΎΡΡΡ log P Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ, Π° ΡΠ°ΠΊΠΎΠΆ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ ΡΠ° Π²ΡΠ»ΡΠ½ΠΈΡ
Π΅Π½Π΅ΡΠ³ΡΠΉ ΠΡΠ±Π±ΡΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² ΠΊΠ°Π»ΡΠΊΡaΡΠ΅Π½Ρ Π· Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ. Π ΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½Ρ Π·Π½Π°ΡΠ΅Π½Π½Ρ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ ΡΠ° Π²ΡΠ»ΡΠ½ΠΈΡ
Π΅Π½Π΅ΡΠ³ΡΠΉ ΠΡΠ±Π±ΡΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² 5,17-Π±ΡΡ-(N ΡΠΎΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ Π· Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ Π·Π½Π°Ρ
ΠΎΠ΄ΡΡΡΡΡ Π² ΠΌΠ΅ΠΆΠ°Ρ
335-910 Π-1 ΡΠ° -14.38 β -16.85 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ, Π²ΡΠ΄ΠΏΠΎΠ²ΡΠ΄Π½ΠΎ. ΠΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΠΎ Π²ΠΏΠ»ΠΈΠ² Π»ΡΠΏΠΎΡΡΠ»ΡΠ½ΠΎΡΡΡ log P ΡΠ° ΡΠΠ° Π·Π°ΠΌΡΡΠ΅Π½ΠΈΡ
Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ Π½Π° ΠΊΠΎΠ½ΡΡΠ°Π½ΡΠΈ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ KA ΡΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² Π· ΠΊΠ°Π»ΡΠΊΡaΡΠ΅Π½ΠΎΠΌ. ΠΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΠΎ ΠΊΠΎΠ½ΡΡΠ°Π½ΡΠΈ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ KA Π·Π±ΡΠ»ΡΡΡΡΡΡΡΡ ΠΏΠΎ ΠΌΡΡΡ Π·Π½ΠΈΠΆΠ΅Π½Π½Ρ Π·Π½Π°ΡΠ΅Π½Ρ Π»ΡΠΏΠΎΡΡΠ»ΡΠ½ΠΎΡΡΡ log P ΡΠ° ΡΠΠ° Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ. ΠΡΠΎΠ²Π΅Π΄Π΅Π½ΠΎ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½Π΅ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² Π²ΠΊΠ»ΡΡΠ΅Π½Π½Ρ, ΡΠΊΠ΅ Π²ΠΊΠ°Π·ΡΡ Π½Π° Π½Π°ΡΠ²Π½ΡΡΡΡ Π²ΠΎΠ΄Π½Π΅Π²ΠΈΡ
Π·Π²βΡΠ·ΠΊΡΠ² ΠΌΡΠΆ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΠΈΠΌΠΈ Π³ΡΡΠΏΠ°ΠΌΠΈ Π±Π΅Π½Π·ΠΎΠΉΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ ΡΠ° Π°ΡΠΎΠΌΠ°ΠΌΠΈ Π²ΠΎΠ΄Π½Ρ iΠΌΡΠ½ΠΎΠ³ΡΡΠΏ Π²Π΅ΡΡ
Π½ΡΠΎΠ³ΠΎ Π²ΡΠ½ΡΡ Π°Π±ΠΎ Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ½Ρ Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠ»ΡΠ½ΠΈΡ
Π³ΡΡΠΏ Π½ΠΈΠΆΠ½ΡΠΎΠ³ΠΎ Π²ΡΠ½ΡΡ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½ΠΎΠ²ΠΎΠ³ΠΎ ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»Ρ. ΠΡΠ½ΡΠΉΠ½Π° Π·Π°Π»Π΅ΠΆΠ½ΡΡΡΡ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ Π²ΡΠ΄ Π»ΡΠΏΠΎΡΡΠ»ΡΠ½ΠΎΡΡΡ log P ΠΊΠΈΡΠ»ΠΎΡ Π²ΠΊΠ°Π·ΡΡ Π½Π° ΠΏΠΎΠΌΡΡΠ½Ρ ΡΠΎΠ»Ρ ΡΠΎΠ»ΡΠ²Π°ΡΠΎΡΠΎΠ±Π½ΠΈΡ
Π²Π·Π°ΡΠΌΠΎΠ΄ΡΠΉ ΠΏΡΠΈ ΡΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ Π· 5,17-Π±ΡΡ-(N-ΡΠΎΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)- 25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½ΠΎΠΌ
INCREASING THE SOLUBILITY OF DIPYRIDAMOLE USING POLYETHYLENE GLYCOLS
Objective: The objective of the present study is a determination of the limiting solubility of dipyridamole in water and optimal ratios of polyethylene glycol:dipyridamole at which formation of solid dispersion is observed.
Methods: UV-spectroscopy was used to determine the effect of polymer on limiting solubility of dipyridamole. Using low-temperature differential scanning calorimetry (DSC), it was made possible to obtain solid dispersions of dipyridamole with polyethylene glycols having average molecular weight 1000 and 1400.
Results: The optimal ratio of polymer:Drug is 1:1, and is 3:1 for PEG-1000 and PEG-1400 respectively. Joint dissolution of dipyridamole with PEG-1400 and PEG-1000 increases the drug content in the water by up to 8.1 times and up to 175 times, compared with the solution containing only dipyridamole.
Conclusion: using systems based on dipyridamole and polyethylene glycol with average molecular weight of 1000, may increase the bioavailability of the drug and consequently reduce the dosages. Wide range of ratios, in which the formation of solid dispersions is possible, enables to adjust the solubility of dipyridamole in neutral aqueous media
ΠΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½Π½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ ΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ ΡΠ° ΠΊΠ°Π»ΡΠΊΡ[4]ΡΠ΅Π·ΠΎΡΡΠΈΠ½Π°ΡΠ΅Π½Ρ ΡΠ· ΡΠΌΠΎΠ»ΡΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΠ€ ΠΠΠ Π₯. ΠΠΈΠ·Π½Π°ΡΠ΅Π½Π½Ρ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ
The Host-Guest complexation of octakis-(diphenoxyphosphoryloxy)tetramethylcalix[4]resorcinarene (CR) and 5,17-bis-(N-tolyliminomethyl)-25,27-dipropoxycalix[4]arene (CA) with 6 diterpenoid (resin) acids has been studied by the reversed phase high-performance liquid chromatography (RP HPLC). The chromatographic characteristics (retention time tR and retention factor kβ) of resin acids have been determined. The lipophilicity values log P of the acids, binding constants KA (395-682 M-1 for CR and 844-1268 M-1 for CA), as well as Gibbs free energies βG (-14.79 β -16.14 kJ/mol for CR and -16.70 β -17.67 kJ/mol for CA) of the complexes with resin acids have been calculated. Molecular modelling of CA complexes has revealed the presence of hydrogen bonds between carboxylic groups of acids and nitrogen atoms of imino groups at the upper rim or oxygen atoms of the hydroxyl groups at the lower rim of the CA macrocycle. Molecular modelling of CR complexes has shown the presence of hydrogen bonds between carboxylic groups of acids and oxygen atoms of diphenoxyphosphoryloxy groups at the upper rim of the CR macrocycle. The effect of log P values on KA values of the CR/CA complexes has been assessed. The linear dependence of the binding constants on the acid lipophilicity indicates a significant role of solvophobic interactions on the complexation. The relationship between supramolecular (KA) and physicochemical (log P, pKa) characteristics of acids has been determined.ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΠ΅ ΡΠΈΠΏΠ° ΠΠΎΡΡΡ-Π₯ΠΎΠ·ΡΠΈΠ½ oΠΊΡΠ°ΠΊΠΈΡ-(Π΄ΠΈΡΠ΅Π½ΠΎΠΊΡΠΈΡΠΎΡΡΠΎΡΠΈΠ»ΠΎΠΊΡΠΈ)-ΡΠ΅ΡΡΠ°ΡΡΠΈΠ»ΠΊΠ°Π»ΠΈΠΊΡ[4]ΡΠ΅Π·ΠΎΡΡΠΈΠ½Π°ΡΠ΅Π½Π° (CR) ΠΈ 5,17-Π±ΠΈΡ-(N-ΡΠΎΠ»ΠΈΠ»ΠΈΠΌΠΈΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΠΈΠΊΡ[4]aΡΠ΅Π½Π° (CA) Ρ 6 Π΄ΠΈΡΠ΅ΡΠΏΠ΅Π½ΠΎΠΈΠ΄Π½ΡΠΌΠΈ ( ΡΠΌΠΎΠ»ΡΠ½ΡΠΌΠΈ) ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ Π±ΡΠ»ΠΎ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΎ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΎΠ±ΡΠ°ΡΠ΅Π½Π½ΠΎ-ΡΠ°Π·Π½ΠΎΠΉ Π²ΡΡΠΎΠΊΠΎΡΡΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΠΉ ΠΆΠΈΠ΄ΠΊΠΎΡΡΠ½ΠΎΠΉ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΠΈ (ΠΠ€ ΠΠΠΠ₯). ΠΠΏΡΠ΅Π΄Π΅Π»Π΅Π½Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠΈ (Π²ΡΠ΅ΠΌΡ ΡΠ΄Π΅ΡΠΆΠΈΠ²Π°Π½ΠΈΡ tR ΠΈ ΡΠ°ΠΊΡΠΎΡ ΡΠ΄Π΅ΡΠΆΠΈΠ²Π°Π½ΠΈΡ kβ) ΡΠΌΠΎΠ»ΡΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ. Π Π°ΡΡΡΠΈΡΠ°Π½Ρ Π·Π½Π°ΡΠ΅Π½ΠΈΡ Π»ΠΈΠΏΠΎΡΠΈΠ»ΡΠ½ΠΎΡΡΠΈ log P ΡΠΌΠΎΠ»ΡΠ½ΡΡ
ΠΊΠΈΡΠ»ΠΎΡ ΠΈ ΠΊΠΎΠ½ΡΡΠ°Π½Ρ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ KA ΠΈΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² (395-682 Π-1 Π΄Π»Ρ CR ΠΈ 844-1268 Π-1 Π΄Π»Ρ CA), Π° ΡΠ°ΠΊΠΆΠ΅ Π·Π½Π°ΡΠ΅Π½ΠΈΡ ΡΠ²ΠΎΠ±ΠΎΠ΄Π½ΡΡ
ΡΠ½Π΅ΡΠ³ΠΈΠΉ ΠΠΈΠ±Π±ΡΠ° βG (-14.79 β -16.14 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ Π΄Π»Ρ CR ΠΈ -16.70 β -17.67 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ Π΄Π»Ρ CAL) ΡΠΎ ΡΠΌΠΎΠ»ΡΠ½ΡΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ. ΠΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎΠ΅ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² CA ΠΏΠΎΠΊΠ°Π·Π°Π»ΠΎ Π½Π°Π»ΠΈΡΠΈΠ΅ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π½ΡΡ
ΡΠ²ΡΠ·Π΅ΠΉ ΠΌΠ΅ΠΆΠ΄Ρ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΡΠΌΠΈ Π³ΡΡΠΏΠΏΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡ ΠΈ Π°ΡΠΎΠΌΠ°ΠΌΠΈ Π°Π·ΠΎΡΠ° ΠΈΠΌΠΈΠ½ΠΎ-Π³ΡΡΠΏΠΏ Π²Π΅ΡΡ
Π½Π΅Π³ΠΎ ΠΎΠ±ΠΎΠ΄Π°Β ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»Π° CA ΠΈΠ»ΠΈ Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄Π° Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠ»ΡΠ½ΡΡ
Π³ΡΡΠΏΠΏ Π΅Π³ΠΎ Π½ΠΈΠΆΠ½Π΅Π³ΠΎ ΠΎΠ±ΠΎΠ΄Π°. ΠΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎΠ΅ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² CR ΠΏΠΎΠΊΠ°Π·Π°Π»ΠΎ Π½Π°Π»ΠΈΡΠΈΠ΅ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π½ΡΡ
ΡΠ²ΡΠ·Π΅ΠΉ ΠΌΠ΅ΠΆΠ΄Ρ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΡΠΌΠΈ Π³ΡΡΠΏΠΏΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡ ΠΈ Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠΎΠ΄Π° Π΄ΠΈΡΠ΅Π½ΠΎΠΊΡΠΈΡΠΎΡΡΠΎΡΠΈΠ»ΠΎΠΊΡΠΈ-Π³ΡΡΠΏΠΏ Π²Π΅ΡΡ
Π½Π΅Π³ΠΎ ΠΎΠ±ΠΎΠ΄Π° ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»Π° CR. ΠΡΠ΅Π½Π΅Π½ΠΎ Π²Π»ΠΈΡΠ½ΠΈΠ΅ log P Π½Π° ΠΊΠΎΠ½ΡΡΠ°Π½ΡΡ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ KA ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² CR/CA. ΠΠΈΠ½Π΅ΠΉΠ½Π°Ρ Π·Π°Π²ΠΈΡΠΈΠΌΠΎΡΡΡ ΠΠ ΠΎΡ log P ΠΊΠΈΡΠ»ΠΎΡ ΡΠ²ΠΈΠ΄Π΅ΡΠ΅Π»ΡΡΡΠ²ΡΠ΅Ρ ΠΎ Π²Π»ΠΈΡΠ½ΠΈΠΈ ΡΠΎΠ»ΡΠ²ΠΎΡΠΎΠ±Π½ΡΡ
Π²Π·Π°ΠΈΠΌΠΎΠ΄Π΅ΠΉΡΡΠ²ΠΈΠΉ Π½Π° ΠΏΡΠΎΡΠ΅ΡΡ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΡ.ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ ΡΠΈΠΏΡ ΠΡΡΡΡ-ΠΠΎΡΠΏΠΎΠ΄Π°Ρ oΠΊΡΠ°ΠΊΡΡ-(Π΄ΠΈΡΠ΅Π½ΠΎΠΊΡΠΈΡΠΎΡΡΠΎΡΠΈΠ»ΠΎΠΊΡΠΈ)-ΡΠ΅ΡΡΠ°ΠΌΠ΅ΡΠΈΠ»ΠΊΠ°Π»ΡΠΊΡ[4]ΡΠ΅Π·ΠΎΡΡΠΈΠ½Π°ΡΠ΅Π½Ρ (CR) ΡΠ° 5,17-Π±ΡΡ-(N-ΡΠΎΠ»ΡΠ»ΡΠΌΡΠ½ΠΎΠΌΠ΅ΡΠΈΠ»)-25,27-Π΄ΠΈΠΏΡΠΎΠΏΠΎΠΊΡΠΈΠΊΠ°Π»ΡΠΊΡ[4]aΡΠ΅Π½Ρ (CA) Π· 6 Π΄ΠΈΡΠ΅ΡΠΏΠ΅Π½ΠΎΡΠ΄Π½ΠΈΠΌΠΈ (ΡΠΌΠΎΠ»ΡΠ½ΠΈΠΌΠΈ) ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ Π±ΡΠ»ΠΎ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΠΎ ΠΌΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΎΠ±Π΅ΡΠ½Π΅Π½ΠΎ-ΡΠ°Π·Π½ΠΎΡ Π²ΠΈΡΠΎΠΊΠΎΠ΅ΡΠ΅ΠΊΡΠΈΠ²Π½ΠΎΡ ΡΡΠ΄ΠΈΠ½Π½ΠΎΡ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡ (ΠΠ€ ΠΠΠ Π₯). ΠΠΈΠ·Π½Π°ΡΠ΅Π½Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡΠ½Ρ Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠΈ (ΡΠ°Ρ ΡΡΡΠΈΠΌΠ°Π½Π½Ρ tR Ρa ΡΠ°ΠΊΡΠΎΡ ΡΡΡΠΈΠΌΠ°Π½Π½Ρ kβ) ΡΠΌΠΎΠ»ΡΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ. Π ΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½ΠΎ Π·Π½Π°ΡΠ΅Π½Π½Ρ Π»ΡΠΏΠΎΡΡΠ»ΡΠ½ΠΎΡΡΡ log P ΡΠΌΠΎΠ»ΡΠ½ΠΈΡ
ΠΊΠΈΡΠ»ΠΎΡ Ρa ΠΊΠΎΠ½ΡΡΠ°Π½Ρ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ KA ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² (395-682 Π-1 Π΄Π»Ρ CR Ρa 844-1268 Π-1 Π΄Π»Ρ CA), Π° ΡΠ°ΠΊΠΎΠΆ Π·Π½Π°ΡΠ΅Π½Π½Ρ Π²ΡΠ»ΡΠ½ΠΈΡ
Π΅Π½Π΅ΡΠ³ΡΠΉ ΠΡΠ±Π±ΡΠ° βG (-14.79 β -16.14 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ Π΄Π»Ρ CR Ρa -16.70 β -17.67 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ Π΄Π»Ρ CA) ΡΠ· ΡΠΌΠΎΠ»ΡΠ½ΠΈΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡΠ°ΠΌΠΈ. ΠΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½Π΅ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² CA Π²ΠΊΠ°Π·Π°Π»ΠΎ Π½Π° ΠΏΡΠΈΡΡΡΠ½ΡΡΡΡ Π²ΠΎΠ΄Π½Π΅Π²ΠΈΡ
Π·Π²βΡΠ·ΠΊΡΠ² ΠΌΡΠΆ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΠΈΠΌΠΈ Π³ΡΡΠΏΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡ Ρa Π°ΡΠΎΠΌΠ°ΠΌΠΈ Π°Π·ΠΎΡΡ ΡΠΌΡΠ½ΠΎ-Π³ΡΡΠΏ Π²Π΅ΡΡ
Π½ΡΠΎΠ³ΠΎ Π²ΡΠ½ΡΡ CA ΠΌΠ°ΠΊΡΠΎΡΠΈΠ»Ρ Π°Π±ΠΎ Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ½Ρ ΠΠ Π³ΡΡΠΏ ΠΉΠΎΠ³ΠΎ Π½ΠΈΠΆΠ½ΡΠΎΠ³ΠΎ Π²ΡΠ½ΡΡ. ΠΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½Π΅ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² CR Π²ΠΊΠ°Π·Π°Π»ΠΎ Π½Π° ΠΏΡΠΈΡΡΡΠ½ΡΡΡΡ Π²ΠΎΠ΄Π½Π΅Π²ΠΈΡ
Π·Π²βΡΠ·ΠΊΡΠ² ΠΌΡΠΆ ΠΊΠ°ΡΠ±ΠΎΠΊΡΠΈΠ»ΡΠ½ΠΈΠΌΠΈ Π³ΡΡΠΏΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡ Ρa Π°ΡΠΎΠΌΠ°ΠΌΠΈ ΠΊΠΈΡΠ½Ρ Π΄ΠΈΡΠ΅Π½ΠΎΠΊΡΠΈΡΠΎΡΡΠΎΡΠΈΠ»ΠΎΠΊΡΠΈ-Π³ΡΡΠΏ Π²Π΅ΡΡ
Π½ΡΠΎΠ³ΠΎ Π²ΡΠ½ΡΡ ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»Ρ CR. ΠΠ΄ΡΠΉΡΠ½Π΅Π½ΠΎ ΠΎΡΡΠ½ΠΊΡ Π²ΠΏΠ»ΠΈΠ²Ρ log P Π½Π° ΠΊΠΎΠ½ΡΡΠ°Π½ΡΠΈ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ KA ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² CR/CA. ΠΡΠ½ΡΠΉΠ½Π° Π·Π°Π»Π΅ΠΆΠ½ΡΡΡΡ ΠΠ Π²ΡΠ΄ log P ΠΊΠΈΡΠ»ΠΎΡ Π²ΠΊΠ°Π·ΡΡ Π½Π° ΡΠΎΠ»Ρ ΡΠΎΠ»ΡΠ²ΠΎΡΠΎΠ±Π½ΠΈΡ
Π²Π·Π°ΡΠΌΠΎΠ΄ΡΠΉ Π½Π° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ. ΠΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ Π²Π·Π°ΡΠΌΠΎΠ·Π²βΡΠ·ΠΎΠΊ ΠΌΡΠΆ ΡΡΠΏΡΠ°ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΈΠΌΠΈ (KA) Ρa ΡΡΠ·ΠΈΠΊΠΎ-Ρ
ΡΠΌΡΡΠ½ΠΈΠΌΠΈ (log P, pKa) Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΡΡΠΈΠΊΠ°ΠΌΠΈ ΠΊΠΈΡΠ»ΠΎΡ
Selective preparation of beta-cyclodextrin clathrates by solid-phase exchange of included tetrahydrofurane for volatile guests in absence of water
Β© 2014 AkadΓ©miai KiadΓ³, Budapest, Hungary. Solid-phase guest-exchange products, prepared from dehydrated clathrate of beta-cyclodextrin (bCD) with tetrahydrofurane (THF) by its saturation with vapor of second guest, were studied using thermal analysis by thermogravimetry combined with mass-spectrometric detection of evolved vapors. This guest-exchange procedure was found to be effective for inclusion of volatile guests, which otherwise require a difficult optimization of preparation conditions. Besides, a performed solid-phase exchange without liquid/solid-phase contact is a standard, technologically friendly procedure of clathrate preparation, which does not require further drying to provide an end product. An observed exchange of THF in the absence of water is rather selective, with some hydrophobic guests being unable to replace THF in its dried clathrate with bCD. This selectivity together with low toxicity of THF may be an advantage for practical applications of this guest-exchange method
Molecular recognition of organic guest vapor by solid adamantylcalix[4] arene
A series of inclusion compounds prepared by saturation of the solid adamantyl[4]calixarene (host 1) with vaporous organic guests at 298 K was studied by thermal gravimetry and static headspace GC analyses. The sorption isotherms of guests by host 1, the stoichiometry of the guest-host inclusion compounds, and the Gibbs energies of their formation were determined. The data obtained give evidence of the molecular recognition of the guest shape by host 1. Hence, compound 1 can be used in sensors for recognizing volatile organic compounds with no strong hydrogen or donor-acceptor bonds involved
A calorimetric study of the formation of phenacetin solid dispersions with PEG-1400 and pluronic F127
The formation of solid dispersions is one of the methods of drug hydrophilization. The method of low-temperature differential scanning calorimetry showed the possibility to obtain phenacetin solid dispersions with polyethylene glycol and Pluronic F127. The method of low-temperature differential scanning calorimetry proved that when the polymer/phenacetin ratio is 10:1, the crystalline phase of the drug is not fixed, while when the ratio is 1:1 the pharmacological component exhibits the properties of a separate phase and does not form a solid dispersion. Phenacetin does not exhibit plastifying action and does not change the thermophysical properties of polymer phase that can facilitate an easy release of the drug from the composite. Β© IDOSI Publications, 2013
ΠΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ ΠΊΠ°Π»ΡΠΊΡ[4]Π°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»-ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ Π· ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΡΠ° N-aΡΠ΅ΡΠΈΠ»-ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄ΠΎΠΌ
The Host-Guest complexation of calixarene hydroxymethylphosphonic acid with tryptophan and N-acetyltryptophan amide has been investigated by the RP HPLC method in H2O/MeCN (99/1) solution (column support Hypersil CN, UV-detector, Ξ» = 254 nm). Adsorption of calixarene hydroxymethylphosphonic acid on the Hypersil CN surface has been studied. It has been found that hydroxymethylphosphonic acid is characterized by reversible sorption on the Hypersil CN surface. The binding constants (KA = 23000 M-1 and 39000 M-1 for tryptophan and N-acetyltryptophan amide, respectively) of the supramolecular complexes have been calculated from the ratio between the capacity factors kβ of the Guest and the calixarene hydroxymethylphosphonic acid Host concentration in the mobile phase. The Gibbs free energies of the tryptophan and N-acetyltryptophan amide complexes are -24.84 and -26.15 kJ/mol, respectively. The molecular modelling of calixarene hydroxymethylphosphonic acid and its complexes with tryptophan and N-acetyltryptophan amide (Hyper Chem, version 8, force field PM3) has indicated that the complexes are stabilized by hydrogen bonds, electrostatic, Ο-Ο, and solvatophobic interactions. The geometric parameters of the energy minimized calixarene macrocycle and its complexes with tryptophan and N-acetyltryptophan amide have been calculated. According to the calculations it has been shown that the Host-Guest complexation does not change the flattened-cone conformation of calixarene. Finally, the inverse correlation has been found between the KA values of the complexes and the Log P values of the guest molecules.ΠΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΠ€ ΠΠΠΠ₯ ΠΈΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ ΠΏΡΠΎΡΠ΅ΡΡ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΡ ΡΠΈΠΏΠ° Π₯ΠΎΠ·ΡΠΈΠ½-ΠΠΎΡΡΡ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΠΈ N-aΡΠ΅ΡΠΈΠ»-ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΠΈΠ΄ΠΎΠΌ Π² ΡΠ°ΡΡΠ²ΠΎΡΠ΅ H2O/MeCN (99/1) (Π½Π°ΡΠ°Π΄ΠΊΠ° Hypersil CN, Π£Π€-Π΄Π΅ΡΠ΅ΠΊΡΠΎΡ, Ξ» = 254 Π½ΠΌ). ΠΡΡΠ»Π΅Π΄ΠΎΠ²Π°Π½ΠΎ Π²Π·Π°ΠΈΠΌΠΎΠ΄Π΅ΠΉΡΡΠ²ΠΈΠ΅ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ Ρ ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΡΡ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΎΠΉ Π½Π°ΡΠ°Π΄ΠΊΠΈ Hypersil CN. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²Π°Ρ ΠΊΠΈΡΠ»ΠΎΡΠ° Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΠ·ΡΠ΅ΡΡΡ ΠΎΠ±ΡΠ°ΡΠΈΠΌΠΎΠΉ ΡΠΎΡΠ±ΡΠΈΠ΅ΠΉ Π½Π° ΠΏΠΎΠ²Π΅ΡΡ
Π½ΠΎΡΡΠΈ Hypersil CN. ΠΠΎΠ½ΡΡΠ°Π½ΡΡ ΡΠ²ΡΠ·ΡΠ²Π°Π½ΠΈΡ ΡΡΠΏΡΠ°ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΡΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² (23000 M-1 ΠΈ 39000 M-1 Π΄Π»Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π° ΠΈ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΠΈΠ΄Π°, ΡΠΎΠΎΡΠ²Π΅ΡΡΡΠ²Π΅Π½Π½ΠΎ) Π±ΡΠ»ΠΈ ΡΠ°ΡΡΡΠΈΡΠ°Π½Ρ ΠΈΠ· ΡΠΎΠΎΡΠ½ΠΎΡΠ΅Π½ΠΈΡ ΠΌΠ΅ΠΆ- Π΄Ρ ΠΊΠΎΡΡΡΠΈΡΠΈΠ΅Π½ΡΠΎΠΌ Π΅ΠΌΠΊΠΎΡΡΠΈ kβ ΠΌΠΎΠ»Π΅ΠΊΡΠ»Ρ ΠΠΎΡΡΡ ΠΈ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΠΈΠ΅ΠΉ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΒΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ Π₯ΠΎΠ·ΡΠΈΠ½Π° Π² ΠΏΠΎΠ΄Π²ΠΈΠΆΠ½ΠΎΠΉ ΡΠ°Π·Π΅. ΠΠ½Π°ΡΠ΅Π½ΠΈΡ ΡΠ²ΠΎΠ±ΠΎΠ΄Π½ΡΡ
ΡΠ½Π΅ΡΠ³ΠΈΠΉ ΠΠΈΠ±Π±ΡΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² ΠΊΠ°Π»ΠΈΠΊΡΠ°ΒΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΠΈ N-aΡΠ΅ΡΠΈΠ»-ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΠΈΠ΄ΠΎΠΌ ΡΠΎΡΡΠ°Π²ΠΈΠ»ΠΈ -24.84 ΠΈ -26.15 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ, ΡΠΎΠΎΡΠ²Π΅ΡΡΡΠ²Π΅Π½Π½ΠΎ. ΠΡΠΎΠ²Π΅Π΄Π΅Π½ΠΎ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΎΠ΅ ΠΌΠΎΠ΄Π΅Π»ΠΈΡΠΎΠ²Π°Π½ΠΈΠ΅ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈ- ΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ ΠΈ Π΅Π΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΠΈ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΠΈΠ΄ΠΎΠΌ (Hyper Chem, Π²Π΅ΡΡΠΈΡ 8, ΡΠΈΠ»ΠΎΠ²ΠΎΠ΅ ΠΏΠΎΠ»Π΅ PM3). ΠΡΠΌΠ΅ΡΠ°Π΅ΡΡΡ, ΡΡΠΎ ΡΡΠΏΡΠ°ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΡΠ΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡ ΠΌΠΎΠ³ΡΡ ΡΡΠ°Π±ΠΈΠ»ΠΈΠ·ΠΈΡΠΎΠ²Π°ΡΡΡΡ Π²ΠΎΠ΄ΠΎΡΠΎΠ΄Π½ΡΠΌΠΈ ΡΠ²ΡΠ·ΡΠΌΠΈ, Π° ΡΠ°ΠΊΠΆΠ΅ ΡΠ»Π΅ΠΊΡΡΠΎΡΡΠ°ΡΠΈΡΠ΅ΡΠΊΠΈΠΌΠΈ, Ο-Ο, ΠΈ ΡΠΎΠ»ΡΠ²Π°ΡΠΎΡΠΎΠ±Π½ΡΠΌΠΈ Π²Π·Π°ΠΈΠΌΠΎΠ΄Π΅ΠΉΡΡΠ²ΠΈΡΠΌΠΈ. Π Π°ΡΡΡΠΈΡΠ°Π½Ρ Π³Π΅ΠΎΠΌΠ΅ΡΡΠΈΡΠ΅ΡΠΊΠΈΠ΅ ΠΏΠ°ΡΠ°ΠΌΠ΅ΡΡΡ ΡΠ½Π΅ΡΠ³Π΅ΡΠΈΡΠ΅ΡΠΊΠΈ ΠΌΠΈΠ½ΠΈΠΌΠΈΠ·ΠΈΡΠΎΠ²Π°Π½Π½ΡΡ
ΡΡΡΡΠΊΡΡΡ ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π³ΠΈΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΠΉ ΠΊΠΈΡΠ»ΠΎΡΡ ΠΈ Π΅Π΅ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠ² Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΠΈ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΠΈΠ΄ΠΎΠΌ. Π‘ΠΎΠ³Π»Π°ΡΠ½ΠΎ ΡΠ°ΡΡΠ΅ΡΠ°ΠΌ ΠΏΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΡΠΎ ΠΏΡΠΎΡΠ΅ΡΡ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΠΎΠ±ΡΠ°Π·ΠΎΠ²Π°Π½ΠΈΡ Π½Π΅ ΠΌΠ΅Π½ΡΠ΅Ρ ΠΊΠΎΠ½ΡΠΎΡΠΌΠ°ΡΠΈΡ ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»ΠΈΡΠ΅ΡΠΊΠΎΠ³ΠΎ ΠΎΡΡΠΎΠ²Π° ΠΊΠ°Π»ΠΈΠΊΡΠ°ΡΠ΅Π½Π°. Π£ΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΡΠΎ Π·Π½Π°ΡΠ΅Π½ΠΈΡ KA ΠΏΠΎΠ²ΡΡΠ°ΡΡΡΡ ΡΠΎ ΡΠ½ΠΈΠΆΠ΅Π½ΠΈΠ΅ΠΌ Log P ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΠΠΎΡΡΠ΅ΠΉ.ΠΠ΅ΡΠΎΠ΄ΠΎΠΌ ΠΠ€ ΠΠΠ Π₯ Π΄ΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΠΎ ΠΏΡΠΎΡΠ΅Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ ΡΠΈΠΏΡ ΠΠΎΡΠΏΠΎΠ΄Π°Ρ-ΠΡΡΡΡ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈ- ΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ Π· ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ ΡΠ° N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄ΠΎΠΌ Ρ ΡΠΎΠ·ΡΠΈΠ½Ρ H2O/MeCN (99/1) (Π½Π°ΡΠ°Π΄ΠΊΠ° Hypersil CN, Π£Π€-Π΄Π΅ΡΠ΅ΠΊΡΠΎΡ, Ξ» = 254 Π½ΠΌ). ΠΠΎΡΠ»ΡΠ΄ΠΆΠ΅Π½ΠΎ Π²Π·Π°ΡΠΌΠΎΠ΄ΡΡ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ Π· ΠΏΠΎΠ²Π΅ΡΡ
Π½Π΅Ρ Ρ
ΡΠΎΠΌΠ°ΡΠΎΠ³ΡΠ°ΡΡΡΠ½ΠΎΡ Π½Π°ΡΠ°Π΄ΠΊΠΈ Hypersil CN. ΠΡΡΠ°Π½ΠΎΠ²Π»Π΅Π½ΠΎ, ΡΠΎ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²Π° ΠΊΠΈΡΠ»ΠΎΡΠ° Ρ
Π°ΡΠ°ΠΊΡΠ΅ΡΠΈΠ·ΡΡΡΡΡΡ ΠΎΠ±Π΅ΡΠ½Π΅Π½ΠΎΡ ΡΠΎΡΠ±ΡΡΡΡ Π½Π° ΠΏΠΎΠ²Π΅ΡΡ
Π½Ρ Hypersil CN. ΠΠΎΠ½- ΡΡΠ°Π½ΡΠΈ Π·Π²βΡΠ·ΡΠ²Π°Π½Π½Ρ ΡΡΠΏΡΠ°ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½ΠΈΡ
ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² (23000 M-1 Ρ 39000 M-1 Π΄Π»Ρ ΡΡΠΈΠΏΡΠΎΡΠ°Π½Ρ Ρ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄Ρ, Π²ΡΠ΄ΠΏΠΎΠ²ΡΠ΄Π½ΠΎ) Π±ΡΠ»ΠΈ ΡΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½Ρ ΡΠ· ΡΠΏΡΠ²Π²ΡΠ΄Π½ΠΎΡΠ΅Π½Π½Ρ ΠΌΡΠΆ ΠΊΠΎΠ΅ΡΡΡΡΡΠ½ΡΠΎΠΌ ΡΠΌΠΊΠΎΡΡΡ kβ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΠΈ ΠΠΎΡΡΡ Ρ ΠΊΠΎΠ½ΡΠ΅Π½ΡΡΠ°ΡΡΡΡ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ ΠΠΎΡΠΏΠΎΠ΄Π°ΡΡ Π² ΡΡΡ
ΠΎΠΌΡΠΉ ΡΠ°Π·Ρ. ΠΠ½Π°ΡΠ΅Π½Π½Ρ Π²ΡΠ»ΡΠ½ΠΈΡ
ΡΠ½Π΅ΡΠ³ΡΠΉ ΠΡΠ±Π±ΡΠ° ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ Π· ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ Ρ N-aΡΠ΅- ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄ΠΎΠΌ ΡΠΊΠ»Π°Π΄Π°Ρ -24.84 Ρ -26.15 ΠΊΠΠΆ/ΠΌΠΎΠ»Ρ, Π²ΡΠ΄ΠΏΠΎΠ²ΡΠ΄Π½ΠΎ. ΠΠ΄ΡΠΉΡΠ½Π΅Π½ΠΎ ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½Π΅ ΠΌΠΎΠ΄Π΅Π»ΡΠ²Π°Π½Π½Ρ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡΠ»ΠΎΡΠΈ Ρ ΡΡ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² Π· ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ Ρ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄ΠΎΠΌ (Hyper Chem, Π²Π΅ΡΡΡΡ 8, ΡΠΈΠ»ΠΎΠ²Π΅ ΠΏΠΎΠ»Π΅ PM3). Π‘ΡΠΏΡΠ°ΠΌΠΎΠ»Π΅ΠΊΡΠ»ΡΡΠ½Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΈ ΠΌΠΎΠΆΡΡΡ ΡΡΠ°Π±ΡΠ»ΡΠ·ΡΠ²Π°ΡΠΈΡΡ Π²ΠΎΠ΄Π½Π΅Π²ΠΈΠΌΠΈ Π·Π²βΡΠ·ΠΊΠ°ΠΌΠΈ, Π° ΡΠ°ΠΊΠΎΠΆ Π΅Π»Π΅ΠΊΡΡΠΎΡΡΠ°ΡΠΈΡΠ½ΠΈΠΌΠΈ, Ο-Ο, Ρ ΡΠΎΠ»ΡΠ²Π°ΡΠΎΡΠΎΠ±Π½ΠΈΠΌΠΈ Π²Π·Π°ΡΠΌΠΎΠ΄ΡΡΠΌΠΈ. Π ΠΎΠ·ΡΠ°Ρ
ΠΎΠ²Π°Π½Ρ Π³Π΅ΠΎΠΌΠ΅ΡΡΠΈΡΠ½Ρ ΠΏΠ°ΡΠ°ΠΌΠ΅ΡΡΠΈ ΡΠ½Π΅ΡΠ³Π΅ΡΠΈΡΠ½ΠΎ ΠΌΡΠ½ΡΠΌΡΠ·ΠΎΠ²Π°Π½ΠΈΡ
ΡΡΡΡΠΊΡΡΡ ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Π³ΡΠ΄ΡΠΎΠΊΡΠΈΠΌΠ΅ΡΠΈΠ»ΡΠΎΡΡΠΎΠ½ΠΎΠ²ΠΎΡ ΠΊΠΈΡ- Π»ΠΎΡΠΈ ΡΠ° ΡΡ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΡΠ² Π· ΡΡΠΈΠΏΡΠΎΡΠ°Π½ΠΎΠΌ Ρ N-aΡΠ΅ΡΠΈΠ»ΡΡΠΈΠΏΡΠΎΡΠ°Π½Π°ΠΌΡΠ΄ΠΎΠΌ. ΠΠΎΠΊΠ°Π·Π°Π½ΠΎ, ΡΠΎ Π·Π½Π°ΡΠ΅Π½Π½Ρ KA Π·ΡΠΎΡΒΡΠ°ΡΡΡ Π·Ρ Π·Π½ΠΈΠΆΠ΅Π½Π½ΡΠΌ Log P ΠΌΠΎΠ»Π΅ΠΊΡΠ» ΡΡΠ±ΡΡΡΠ°ΡΡΠ², Π° ΠΏΡΠΎΡΠ΅Ρ ΠΊΠΎΠΌΠΏΠ»Π΅ΠΊΡΠΎΡΡΠ²ΠΎΡΠ΅Π½Π½Ρ Π½Π΅ Π·ΠΌΡΠ½ΡΡ ΠΊΠΎΠ½ΡΠΎΡΠΌΠ°ΡΡΡ ΠΌΠ°ΠΊΡΠΎΡΠΈΠΊΠ»ΡΡΠ½ΠΎΠ³ΠΎ ΠΊΡΡΡΡΠΊΠ° ΠΊΠ°Π»ΡΠΊΡΠ°ΡΠ΅Π½Ρ
Glassy Carbon Electrode Modified with Silver Nanodendrites Implemented in Polylactide-Thiacalix[4]arene Copolymer for the Electrochemical Determination of Tryptophan
Β© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Glassy carbon electrode (GCE) was modified by new polymeric materials obtained from oligolactides by cross-linking with tetracarboxylated thiacalix[4]arene in cone, partial cone and 1,3-alternate configurations and then silver was deposited by potential cycling in the pores of the polymer film. The modified electrode showed highly sensitive and selective signal toward tryptophan which was irreversibly oxidized on the coating due to Ag + assisted accumulation in the surface layer. The role of macrocycle configuration and conditions for Ag nanodendrites formation are described. Granulation of the polymer films caused by the macrocycles improves both the conditions for silver deposition and tryptophan determination. The electrochemical sensor developed makes it possible to determine from 0.1 to 100ΞΌM of tryptophan with the limit of detection down to 0.03ΞΌM. No interference with oxidation of other amino acids (phenylalanine, histidine, cysteine and tyrosine) was found. The electrochemical sensor developed was validated in the determination of tryptophan sedative medication "Formula of calmness" in the presence of vitamins B 5 and B 6
Effects of hydration, lipids, and temperature on the binding of the volatile aroma terpenes by Ξ²-lactoglobulin powders
The binding properties of dry proteins are relatively poorly known. Many proteins are present in emulsions and suspensions and also in dry forms. This is particularly true of dairy proteins, which are often stored and sold in powdered form. In the present work, the binding of three terpenes (Ξ±-terpinene, Ξ³-terpinene, and terpinolene), which belong to the basic aroma components, and of decane by powdered Ξ²-lactoglobulin (BLG) was studied at different hydration levels (0.05-0.40 g of H2O/g of protein) and temperatures (298 and 309.5 K), in the presence or absence of lipids and small concentrations of ethanol. Vapor sorption isotherms were determined for these systems by a static method of headspace gas chromatographic analysis. A cooperative effect of hydrophobic hydration was observed for the binding of aroma terpenes and decane by the solid BLG. The temperature increase from 298 to 309.5 K reduced the observed hydration threshold of BLG by 0.05-0.08 g of H2O/g of protein. Lipids (1.2% w/w) in hydrated BLG gave at least a 2-fold increase in its binding affinity for the hydrocarbons studied, and synergic effects of the hydration and lipid on this affinity were observed
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