Синтез аналогов ретиналя ряда спиропиранов, изучение их взаимодействия с бактериоопсином из H. Salinarum

The opportunity of design of analogue retinal with replacement of trimethylhexenic ring of a molecule on spiropyran moiety is shown. Process of interaction of the synthesized retinal analogues with bacterioopsin from apomembrane Halobacterium salinarum and their spectral propertie of formed pigments is investigatedПоказана возможность создания аналогов ретиналя, у которых триметилциклогексеновое кольцо молекулы ретиналя замещено на спиропирановый фрагмент. Исследован процесс взаимодействия синтезированных аналогов ретиналя с бактериоопсином в составе апомембран Halobacterium salinarum и их спектральные свойства образующихся пигментов

Аналитическое вэжх-разделение производных ретиноидов природного и 3,4-дидегидрорядов

The goal of the present study was the development of composition analysis method for vision pigments chromophore groups of different animals with the use of high performance liquid chromatography as well as the development of synthetic method for all-E-3,4-didehydroretinal – one of standard compounds. The all-E-3,4- didehydroretinal synthetic route developed earlier has been polished, and the product structure has been confirmed by physical-chemical analysis methods. The chromatographic separation process of Z-isomers of natural retinal and 3,4-didehydroretinal has been studied under isocratic flow conditions with the use of one and two sequentially connected normal phase columns. Optimal chromatographic conditions have been proposed for the separation and analysis of both retinoid model mixtures and animal eye extracts.В данной работе предложен подход к аналитическому разделению методом ВЭЖХ изомеров природного ретиналя и его 3,4-дидегидропроизводного, что необходимо для создания прямого протокола определения состава хромофорных групп зрительных пигментов различных представителей животных

ПОЛУЧЕНИЕ И ИЗУЧЕНИЕ ФОТОХРОМНОГО ПОВЕДЕНИЯ ЗАМЕЩЕННЫХ 5-ВИНИЛ-6'-НИТРО-1,3,3-ТРИМЕТИЛ-СПИРО(ИНДОЛИНО-2,2'-[2H]-ХРОМЕНОВ)

Few 5-vinyl substituted 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-[2H]chromenes) (6’-nitro-spiropyrans) were synthesized by a one-step method from 5-formyl precursor – 5-formyl-6’-nitro-1,3,3-trimethylspiro(indolino-2,2’- [2H]chromene) (1). 5-Vinyl-6’-nitro-spiropyran (2) was prepared by the Wittig olefination of 1 with an ylide, which was generated by the action of potassium tert-butylate on methyltriphenylphosphonium bromide in THF. E-6’- Nitro-5-(1’’-nitroethene-2’’-yl)-6’-nitro-spiropyran (3) was obtained by heating 1, nitromethane, ethylenediammonium diacetate at 50°С in absolute methanol and inert atmosphere. Compounds 1’’-[6’-nitro-spiropyran-5- yl]-2’’,2’’-dicyanoethylene (4) and E-1’’-[6’-nitro-spiropyran-5-yl]-2’’-cyano-2’’-methoxycarbonylethylene (5) were prepared from initial 1 by reflux in ammonium acetate / glacial acetic acid / benzene mixture with malonodinitrile or methyl 2-cyanoacetate, respectively. The procedure for synthesizing derivatives 2’’,2’’-dimethyl-5’’-(6’-nitrospiropyran-5-yl)methylidene-1’’,3’’-dioxane-4’’,6’’-dion (6) and 5’’,5’’-dimethyl-2’’-(6’-nitro-spiropyran-5-yl)- methylidenecyclohexane-1’’,3’’-dion (7) includes the interaction of Meldrum's acid or dimedone, accordingly, with 5-formyl precursor 1 by heating in ethanol in the presence of piperidine and molecular sieves (to bind the released water). The structures of the prepared compounds and their purity have been confirmed by physico-chemical analysis. A spectral kinetic study of the photochromic properties of the substituted 5-vinyl spiropyrans was carried out in toluene and ethanol solutions. The 5-vinyl-6’-nitro-spiropyran derivatives 2–7 described in this work are of interest for further synthetic transformations.Ряд замещенных 5-винил-6’-нитро-1,3,3-триметилспиро(индолино-2,2’-[2H]-хроменов) был получен одностадийными методами синтеза из 5-формильного предшественника. Структуры полученных соединений подтверждены методами физико-химического анализа. Проведены спектрально-кинетические исследования фотохромного поведения новых 5-винилзамещенных продуктов в растворах толуола и этанола

Гибридные аналоги ретиноидов как инструменты для исследований в области нанобиофотоники

This mini-review presents experimental data obtained by the authors in the context of a cycle of structural-functional research on bionanophotochrome bacteriorhodopsin carried out during the past 10 years. We reviewed the synthetic routes and structure-spectral parameters-properties relationship for a number of series of hybrid retinoid analogs and bacteriorhodopsin analogs based on them.В настоящем мини-обзоре представлены собственные экспериментальные данные, полученные авторами в рамках цикла структурно-функциональных исследований бионанофотохрома бактериородопсина в течение последних 10 лет. Рассмотрены методы получения, свойства и взаимосвязь структура-спектральные параметры в нескольких сериях гибридных аналогов ретиноидов и аналогов бактериородопсина на их основе

Синтез новых 3,5-замещенных изоксазолов с потенциальной антиагрегационной активностью

Two new compounds belonging to 3,5-substituted isoxazoles class were synthesized for the action mechanism investigation and the pharmacophore fragment determination of potential anti-aggregative compounds of this class. An attempt to prepare of 5-phenyl-3-(3-pyridyl)isoxazole by the phase-transfer method was described.Для выявления механизма действия потенциальных антиагрегационных средств класса 3,5-замещенных изоксазолов и определения строения фармакофорного фрагмента были синтезированы два новых соединения этого класса. Апробирована одностадийная схема синтеза соединений класса 5-замещенных пиридилизоксазолов в условиях межфазного катализа

Synthesis retinal analogues of spiropyran derivaties, investigation they interactions with bacteriorhodopsin from H. salinarum

The opportunity of design of analogue retinal with replacement of trimethylhexenic ring of a molecule on spiropyran moiety is shown. Process of interaction of the synthesized retinal analogues with bacterioopsin from apomembrane Halobacterium salinarum and their spectral propertie of formed pigments is investigate

Analytical HPLC-separation of retinoid derivatives of natural and 3,4-didehydro series

The goal of the present study was the development of composition analysis method for vision pigments chromophore groups of different animals with the use of high performance liquid chromatography as well as the development of synthetic method for all-E-3,4-didehydroretinal – one of standard compounds. The all-E-3,4- didehydroretinal synthetic route developed earlier has been polished, and the product structure has been confirmed by physical-chemical analysis methods. The chromatographic separation process of Z-isomers of natural retinal and 3,4-didehydroretinal has been studied under isocratic flow conditions with the use of one and two sequentially connected normal phase columns. Optimal chromatographic conditions have been proposed for the separation and analysis of both retinoid model mixtures and animal eye extracts

SYNTHESIS AND STUDY OF THE PHOTOCHROMIC BEHAVIOR OF SUBSTITUTED 6'-NITRO-1,3,3-TRIMETHYL-5-VINYLSPIRO(INDOLINO-2,2'-[2H]CHROMENES)

Few 5-vinyl substituted 6’-nitro-1,3,3-trimethylspiro(indolino-2,2’-[2H]chromenes) (6’-nitro-spiropyrans) were synthesized by a one-step method from 5-formyl precursor – 5-formyl-6’-nitro-1,3,3-trimethylspiro(indolino-2,2’- [2H]chromene) (1). 5-Vinyl-6’-nitro-spiropyran (2) was prepared by the Wittig olefination of 1 with an ylide, which was generated by the action of potassium tert-butylate on methyltriphenylphosphonium bromide in THF. E-6’- Nitro-5-(1’’-nitroethene-2’’-yl)-6’-nitro-spiropyran (3) was obtained by heating 1, nitromethane, ethylenediammonium diacetate at 50°С in absolute methanol and inert atmosphere. Compounds 1’’-[6’-nitro-spiropyran-5- yl]-2’’,2’’-dicyanoethylene (4) and E-1’’-[6’-nitro-spiropyran-5-yl]-2’’-cyano-2’’-methoxycarbonylethylene (5) were prepared from initial 1 by reflux in ammonium acetate / glacial acetic acid / benzene mixture with malonodinitrile or methyl 2-cyanoacetate, respectively. The procedure for synthesizing derivatives 2’’,2’’-dimethyl-5’’-(6’-nitrospiropyran-5-yl)methylidene-1’’,3’’-dioxane-4’’,6’’-dion (6) and 5’’,5’’-dimethyl-2’’-(6’-nitro-spiropyran-5-yl)- methylidenecyclohexane-1’’,3’’-dion (7) includes the interaction of Meldrum's acid or dimedone, accordingly, with 5-formyl precursor 1 by heating in ethanol in the presence of piperidine and molecular sieves (to bind the released water). The structures of the prepared compounds and their purity have been confirmed by physico-chemical analysis. A spectral kinetic study of the photochromic properties of the substituted 5-vinyl spiropyrans was carried out in toluene and ethanol solutions. The 5-vinyl-6’-nitro-spiropyran derivatives 2–7 described in this work are of interest for further synthetic transformations

Synthesis of new 3,5-substiuted isoxazole derivatives possessing potential anti-aggregative activity

Two new compounds belonging to 3,5-substituted isoxazoles class were synthesized for the action mechanism investigation and the pharmacophore fragment determination of potential anti-aggregative compounds of this class. An attempt to prepare of 5-phenyl-3-(3-pyridyl)isoxazole by the phase-transfer method was described