Развитие и применение метода ХПЯ для изучения спин-селективных реакций радикалов биологически важных молекул в водных растворах
Диссертация
Другим важным аспектом данной работы является исследование влияния скалярного спин-спинового взаимодействия ядер (J) как на зависимость ядерной Ti релаксации от магнитного поля, так и на когерентное перераспределение гиперполяризации (на примере ХПЯ) между ядрами в слабых магнитных полях. В магнитных полях, когда разность химических сдвигов ядер становится сравнимой с константами спин-спинового… Читать ещё >
Содержание
- Глава 1. Литературный обзор
- 1. 1. Роль радикалов триптофана в живой природе и проблемы детектирования
- 1. 2. Неэнзнматическая репарация ДНК и нуклеотидов
- 1. 3. Основы метода ХПЯ с временным разрешением
- 1. 4. Феноменологическое проявление ХПЯ в спектрах ЯМР
- 1. 5. Физико-химические свойства реагентов реакций
- 1. 5. 1. Фотохимические реакции DP с ТгрН
- 1. 5. 2. Фотохимические реакции DP с ТугОН
- 1. 5. 3. Фотохимические реакции DP с GMP
- 1. 5. 4. Внутримолекулярный перенос электрона в дипептиде ТгрН-ТугОН
- 2. 1. Методы исследования
- 2. 1. 1. Описание установки ХПЯ с временным разрешением в магнитном поле 4.7 Тл (vh=200 МГц)
- 2. 1. 2. Описание установки ХПЯ с временным разрешением в магнитном поле 14.1 Тл (vH=600 МГц)
- 2. 1. 3. Описание установки с быстрым переключением поля и регистрацией спектров ЯМР высокого разрешения для измерения Ti релаксации и ХПЯ в различных магнитных полях
- 2. 1. 4. Измерение рН
- 2. 2. Реактивы и растворители
- 3. 1. Теоретическая модель и обоснование линейной зависимости геминальной ХПЯ от констант СТВ
- 3. 2. Условия для пропорциональности ХПЯ константам СТВ
- 3. 3. Анализ спектров *Н и 13С ХПЯ тирозина
- 3. 4. Анализ спектров 'Н и 13С ХПЯ триптофана
- 3. 5. 15NХПЯ аденозин-5-монофосфата
- 4. 1. Восстановление радикала GMP тирозином при различных значениях рН
- 4. 2. Восстановление радикала GMP триптофаном при различных значениях рН
- 5. 1. Дисперсия Ti-релаксации пуриновых нуклеотидов
- 5. 1. 1. ЯМРД необменивающихся протонов пуриновых оснований AMP и GMP
- 5. 1. 2. ЯМРД протонов остатка рибозы в AMP и GMP
- 5. 1. 3. Неэкспоненциальная кинетика релаксации системы связанных спинов
- 5. 2. Когерентное перераспределение ХПЯ в системе спинов, связанных скалярным взаимодействием
- 5. 2. 1. Критерий переноса поляризации
- 5. 2. 2. Когерентный перенос ХПЯ в молекуле AMP
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