Russian Journal of Biological Physics and Chemisrty Russian Journal of Biological Physics and Chemisrty АКТУАЛЬНЫЕ ВОПРОСЫ БИОЛОГИЧЕСКОЙ ФИЗИКИ И ХИМИИ 2499-9962 54261 МЕДИЦИНСКАЯ БИОФИЗИКА И БИОФИЗИЧЕСКАЯ ХИМИЯ MEDICAL BIOPHYSICS AND BIOPHYSICAL CHEMISTRY МЕДИЦИНСКАЯ БИОФИЗИКА И БИОФИЗИЧЕСКАЯ ХИМИЯ STUDY OF THE INTERACTION OF CATIONIC AND ANIONIC POLYMETHINE DYES WITH BILE SALTS (CHOLATES) ИЗУЧЕНИЕ ВЗАИМОДЕЙСТВИЯ КАТИОННЫХ И АНИОННЫХ ПОЛИМЕТИНОВЫХ КРАСИТЕЛЕЙ С СОЛЯМИ ЖЕЛЧНЫХ КИСЛОТ (ХОЛАТАМИ) Татиколов А С Tatikolov A S tatikolov@mail.ru Шведова Л А Shvedova L A Пронкин П Г Pronkin P G Институт биохимической физики им. Н.М. Эмануэля РАН ru N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences (IBCP RAS) ru Институт биохимической физики им. Н.М. Эмануэля РАН ru N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences (IBCP RAS) ru Институт биохимической физики им. Н.М. Эмануэля РАН ru N.M. Emanuel Institute of Biochemical Physics, Russian Academy of Sciences (IBCP RAS) ru 25 03 2018 25 03 2018 3 1 158 162 20 03 2018 20 03 2018 https://rusjbpc.ru/en/nauka/article/54261/view

Изучены спектрально-флуоресцентные и фотохимические свойства полиметиновых красителей анионного 3,3’-ди(g-сульфопропил)-4,5,4’,5’-дибензо-9-этилтиакарбоцианин-бетаина (ДЭЦ) и катионных 3,3’,9-триметилтиакарбоцианина (Cyan 2), 3,3'-ди(b-гидрокси)-9-метилтиакарбоцианина, 3,3'-ди(b-гидрокси)-5,5’-диметокси-9-этилтиакарбоцианина в присутствии биологически важных поверхностно-активных веществ (ПАВ) - солей желчных кислот (холатов) холата натрия (NaC), дезоксихолата натрия (NaDC) и таурохолата натрия (NaTC), а также, для сравнения, додецилсульфата натрия (SDS). При введении ПАВ в раствор ДЭЦ наблюдаются спектральные изменения, обусловленные распадом димеров красителя на цис -мономеры и цис-транс -изомеризацией образующихся мономеров. В то время как в присутствии SDS оба процесса протекают параллельно, обусловлены взаимодействием мономеров красителя с мицеллами и происходят главным образом вблизи критической концентрации мицеллообразования (ККМ), при введении возрастающих концентраций холатов распад димеров на мономеры начинается при гораздо меньших концентрациях, чем цис-транс -конверсия. При этом первый процесс завершается при концентрациях близких к ККМ вторичных мицелл холатов (ККМ2), в то время как второй происходит даже при концентрациях холатов >> ККМ2. Сделан вывод, что ДЭЦ может служить зондом, позволяющим оценить величину ККМ2; спектральные изменения ДЭЦ свидетельствуют о перестройке вторичных мицелл с ростом концентрации холатов. Наблюдается также агрегация ДЭЦ и Cyan 2 на холатах. Поскольку она происходит в области концентраций < ККМ2, матрицами для агрегации могут служить как мономерные молекулы, так и малые ассоциаты и первичные мицеллы холатов. Распад же образовавшихся агрегатов начинается при концентрациях холатов свыше ККМ2 и продолжает происходить при дальнейшем росте их концентрации. При импульсном фотолизе растворов ДЭЦ и Cyan 2 в присутствии холатов наблюдаются процессы фотоизомеризации и образования триплетного состояния красителей.

Spectral-fluorescent and photochemical properties of polymethine dyes anionic 3,3'-di(g-sulfopropyl)-4,5,4',5'-dibenzo-9-ethylthiacarbocyanine-betaine (DEC) and cationic 3,3',9-trimethylthiacarbocyanine (Cyan 2), 3,3'-di(b-hydroxy)-9-methylthiacarbocyanine, 3,3'-di(b-hydroxy)-5,5’-dimethoxy-9-ethylthiacarbocyanine in the presence of biological surfactants (bile salts, cholates) sodium cholate (NaC), sodium deoxycholate (NaDC), sodium taurocholate (NaTC) and, for comparison, sodium dodecyl sulfate (SDS), were studied. Upon introduction of surfactants into DEC solution, changes of dye properties are observed due to decomposition of dye dimers into cis -monomers and cis-trans conversion of the resulting monomers. In the presence of SDS, both processes occur in parallel due to noncovalent interaction of dye monomers with micelles, and mainly occur near the critical micelle concentration (CMC). In contrast, upon introduction of cholates, decomposition of dye dimers into monomers begins at much lower concentrations than cis-trans conversion. The former process is completed at cholate concentrations close to CMC of secondary micelles (CMC2), while the latter occurs even at concentrations >> CMC2. It is concluded that DEC can serve as a probe for estimating CMC2; spectral changes of DEC indicate reorganization of secondary micelles with increasing cholate concentration. Aggregation of DEC and Cyan 2 on cholates is also observed. Since it occurs at concentrations < CMC2, monomeric molecules of cholates, their small associates, and primary micelles serve as matrices for aggregation. Decomposition of the aggregates begins at cholate concentrations > CMC2 and continues at higher cholate concentrations. Upon flash photolysis of solutions of DEC and Cyan 2 in the presence of cholates, photoisomerization and triplet state formation are observed.

 полиметиновые красители димеры агрегаты соли желчных кислот (холаты) мицеллы polymethine dyes dimers aggregates bile salts (cholates) micelles

Tatikolov A.S. Polymethine dyes as spectral-fluorescent probes for biomacromolecules. J. Photochem. Photobiol. C, 2012, vol. 13, pp. 55-90. Tatikolov A.S. Polymethine dyes as spectral-fluorescent probes for biomacromolecules. J. Photochem. Photobiol. C, 2012, vol. 13, pp. 55-90. Viseu M.I., Tatikolov A.S., Correia R.F., Costa S.M.B. Time evolution of monomers and aggregates of a polymethine dye probe the dynamics of model vesicles and micelles. J. Photochem. Photobiol. A, 2014, vol. 280, pp. 54-62. Viseu M.I., Tatikolov A.S., Correia R.F., Costa S.M.B. Time evolution of monomers and aggregates of a polymethine dye probe the dynamics of model vesicles and micelles. J. Photochem. Photobiol. A, 2014, vol. 280, pp. 54-62. Chibisov A.K., Prokhorenko V.I., Görner H. Effects of surfactants on the aggregation behaviour of thiacarbocyanine dyes. Chem. Phys., 1999, vol. 250, pp. 47-60. Chibisov A.K., Prokhorenko V.I., Görner H. Effects of surfactants on the aggregation behaviour of thiacarbocyanine dyes. Chem. Phys., 1999, vol. 250, pp. 47-60. Tatikolov A.S., Costa S.M.B. Effects of normal and reverse molecular environment on the spectral properties, isomerization and aggregation of a hydrophilic cyanine dye. Chem. Phys. Lett., 2001, vol. 346, pp. 233-240. Tatikolov A.S., Costa S.M.B. Effects of normal and reverse molecular environment on the spectral properties, isomerization and aggregation of a hydrophilic cyanine dye. Chem. Phys. Lett., 2001, vol. 346, pp. 233-240. Tatikolov A.S., Costa S.M.B. Photophysics and photochemistry of hydrophilic cyanine dyes in normal and reverse micelles. Photochem. Photobiol. Sci., 2002, vol. 1, pp. 211-218. Tatikolov A.S., Costa S.M.B. Photophysics and photochemistry of hydrophilic cyanine dyes in normal and reverse micelles. Photochem. Photobiol. Sci., 2002, vol. 1, pp. 211-218. Sidorowicz A., Mora C., Jabłonka S., Poła A., Modrzycka T., Mosiadz D., Michalak K. Spectral properties of two betaine-type cyanine dyes in surfactant micelles and in the presence of phospholipids. J. Mol. Struct., 2005, vol. 744-747, pp. 711-716. Sidorowicz A., Mora C., Jabłonka S., Poła A., Modrzycka T., Mosiadz D., Michalak K. Spectral properties of two betaine-type cyanine dyes in surfactant micelles and in the presence of phospholipids. J. Mol. Struct., 2005, vol. 744-747, pp. 711-716. Mukhopadhyay S., Maitra U. Chemistry and biology of bile acids. Curr. Sci., 2004, vol. 87, pp. 1666-1683. Mukhopadhyay S., Maitra U. Chemistry and biology of bile acids. Curr. Sci., 2004, vol. 87, pp. 1666-1683. Li G., McGown L.B. Model for bile salt micellization and solubilization from studies of a “polydisperse” array of fluorescent probes and molecular modeling. J. Phys. Chem., 1994, vol. 98, pp. 13711-13719. Li G., McGown L.B. Model for bile salt micellization and solubilization from studies of a “polydisperse” array of fluorescent probes and molecular modeling. J. Phys. Chem., 1994, vol. 98, pp. 13711-13719. Matsuoka K., Moroi Y. Micelle formation of sodium deoxycholate and sodium ursodeoxycholate (Part 1). Biochim. Biophys. Acta, 2002, vol. 1580, pp. 189-199. Matsuoka K., Moroi Y. Micelle formation of sodium deoxycholate and sodium ursodeoxycholate (Part 1). Biochim. Biophys. Acta, 2002, vol. 1580, pp. 189-199. Ninomiya R., Matsuoka K., Moroi Y. Micelle formation of sodium chenodeoxycholate and solubilization into the micelles: comparison with other unconjugated bile salts. Biochim. Biophys. Acta, 2003, vol. 1634, pp. 116-125. Ninomiya R., Matsuoka K., Moroi Y. Micelle formation of sodium chenodeoxycholate and solubilization into the micelles: comparison with other unconjugated bile salts. Biochim. Biophys. Acta, 2003, vol. 1634, pp. 116-125. Matsuoka K., Suzuki M., Honda C., Endo K., Moroi Y. Micellization of conjugated chenodeoxy- and ursodeoxycholates and solubilization of cholesterol into their micelles: comparison with other four conjugated bile salts species. Chemistry and Physics of Lipids, 2006, vol. 139, pp. 1-10. Matsuoka K., Suzuki M., Honda C., Endo K., Moroi Y. Micellization of conjugated chenodeoxy- and ursodeoxycholates and solubilization of cholesterol into their micelles: comparison with other four conjugated bile salts species. Chemistry and Physics of Lipids, 2006, vol. 139, pp. 1-10. Djavanbakht A., Kale K.M., Zana R. Ultrasonic absorption and density studies of the aggregation in aqueous solutions of bile acid salts. J. Coll. Interf. Sci., 1977, vol. 59, pp. 139-148. Djavanbakht A., Kale K.M., Zana R. Ultrasonic absorption and density studies of the aggregation in aqueous solutions of bile acid salts. J. Coll. Interf. Sci., 1977, vol. 59, pp. 139-148. Lindman B., Kamenka N., Fabre H., Ulmius J., Wieloch T. Aggregation, Aggregate Composition, and Dynamics in Aqueous Sodium Cholate Solutions. J. Coll. Interf. Sci., 1980, vol. 73, pp. 556-565. Lindman B., Kamenka N., Fabre H., Ulmius J., Wieloch T. Aggregation, Aggregate Composition, and Dynamics in Aqueous Sodium Cholate Solutions. J. Coll. Interf. Sci., 1980, vol. 73, pp. 556-565. Carey M.C., Small D.M. Micellar properties of dihydroxy and trihydroxy bile salts: effects of counterion and temperature. J. Coll. Interf. Sci., 1969, vol. 31, pp. 382-396. Carey M.C., Small D.M. Micellar properties of dihydroxy and trihydroxy bile salts: effects of counterion and temperature. J. Coll. Interf. Sci., 1969, vol. 31, pp. 382-396. Mishra S.S., Subuddhi U. Spectroscopic investigation of interaction of Nile Blue A, a potent photosensitizer, with bile salts in aqueous medium. J. Photochem. Photobiol. B, 2014, vol. 141, pp. 67-75. Mishra S.S., Subuddhi U. Spectroscopic investigation of interaction of Nile Blue A, a potent photosensitizer, with bile salts in aqueous medium. J. Photochem. Photobiol. B, 2014, vol. 141, pp. 67-75. Mukerjee P., Moroi Y., Murata M., Yang A.Y.S. Bile salts as atypical surfactants and solubilizers. Hepatology, 1984, vol. 4, pp. 61S-65S. Mukerjee P., Moroi Y., Murata M., Yang A.Y.S. Bile salts as atypical surfactants and solubilizers. Hepatology, 1984, vol. 4, pp. 61S-65S. Anachkov S.E., Danov K.D., Basheva E.S., Kralchevsky P.A., Ananthapadmanabhan K.P. Determination of the aggregation number and charge of ionic surfactant micelles from the stepwise thinning of foam films. Adv. Coll. Interf. Sci., 2012, vol. 183-184, pp. 55-67. Anachkov S.E., Danov K.D., Basheva E.S., Kralchevsky P.A., Ananthapadmanabhan K.P. Determination of the aggregation number and charge of ionic surfactant micelles from the stepwise thinning of foam films. Adv. Coll. Interf. Sci., 2012, vol. 183-184, pp. 55-67. Matsuoka K., Maeda M., Moroi Y. Micelle formation of sodium glyco- and taurocholates and sodium glyco- and taurodeoxycholates and solubilization of cholesterol into their micelles. Colloids and Surfaces B, 2003, vol. 32, pp. 87-95. Matsuoka K., Maeda M., Moroi Y. Micelle formation of sodium glyco- and taurocholates and sodium glyco- and taurodeoxycholates and solubilization of cholesterol into their micelles. Colloids and Surfaces B, 2003, vol. 32, pp. 87-95. Акимкин Т.М., Татиколов А.С., Ярмолюк С.М. Спектрально-флуоресцентное изучение взаимодействия цианиновых красителей Cyan 2 и Cyan 45 с ДНК. Химия высоких энергий, 2011, т. 45, с. 252-259. [Akimkin T.M., Tatikolov A.S., Yarmoluk S.M. Spectral and fluorescent study of the interaction of cyanine dyes Cyan 2 and Cyan 45 with DNA. High Energy Chem., 2011, vol. 45, pp. 222-228. (In Russ.)] Akimkin T.M., Tatikolov A.S., Yarmolyuk S.M. Spektral'no-fluorescentnoe izuchenie vzaimodeystviya cianinovyh krasiteley Cyan 2 i Cyan 45 s DNK. Himiya vysokih energiy, 2011, t. 45, s. 252-259. [Akimkin T.M., Tatikolov A.S., Yarmoluk S.M. Spectral and fluorescent study of the interaction of cyanine dyes Cyan 2 and Cyan 45 with DNA. High Energy Chem., 2011, vol. 45, pp. 222-228. (In Russ.)]