Активность порфиринов металлов, содержащих антиоксидантные 2,6-ди-трет-бутилфенольные заместители, в процессе окисления углеводородов тема диссертации и автореферата по ВАК РФ 02.00.08, кандидат химических наук Герасимова, Ольга Алексеевна

  • Герасимова, Ольга Алексеевна
  • кандидат химических науккандидат химических наук
  • 2013, Москва
  • Специальность ВАК РФ02.00.08
  • Количество страниц 177
Герасимова, Ольга Алексеевна. Активность порфиринов металлов, содержащих антиоксидантные 2,6-ди-трет-бутилфенольные заместители, в процессе окисления углеводородов: дис. кандидат химических наук: 02.00.08 - Химия элементоорганических соединений. Москва. 2013. 177 с.

Оглавление диссертации кандидат химических наук Герасимова, Ольга Алексеевна

СОДЕРЖАНИЕ

4

Глава 1. Обзор литературы

1.1. Порфирины в медицине

1.2. Порфирины металлов - биомиметики активных центров гемовых белков

1.2.1. Биомиметики супероксиддисмутазы на основе порфиринов металлов

1.2.2. Биомиметики оксигеназ на основе порфиринов железа и марганца

1.2.2.1. Биомиметики оксигеназ на основе порфиринов металлов как гомогенные катализаторы

1.2.2.2. Биомиметики оксигеназ на основе иммобилизованных порфиринов железа и марганца как гетерогенные катализаторы

Глава 2. Обсуждение результатов

2.1. Получение порфиринов, иммобилизованных на матрице силикагеля

2.1.1. Синтез и спектральные свойства порфиринов металлов

2.1.2. Синтез и характеристики порфиринов металлов,

иммобилизованных на матрице силикагеля

2.2. Изучение окислительной активности порфиринов металлов

2.2.1. Активность неиммобилизованных порфиринов металлов в процессах окисления углеводородов

2.2.2. Изучение механизма окисления углеводородов №104 в присутствии порфиринов Бе и Мп

2.2.2.1. Образование комплексов порфиринов Бе и Мп с имидазолом

2.2.2.2. Исследование окисления порфиринов Бе и Мп ЫаЮ4 методом электронной спектроскопии поглощения

2.2.2.3. Исследование окисления порфиринов Бе и Мп №Ю4 методом масс-спектрометрии

2.2.2.4. Исследование окисления порфирина Бе с 2,6-ди-трет-бутилфенольными группами методом ЭПР

2.2.3. Активность иммобилизованных порфиринов металлов в процессах окисления углеводородов

2.2.4. Сравнительный анализ механизма окисления углеводородов в присутствии порфиринов Бе и Мп, содержащих 2,6-]щ-трет-бутилфенольные и фенильные заместители

Глава 3. Экспериментальная часть

3.1. Синтез порфиринов

3.2. Иммобилизация порфиринов металлов на матрице силикагеля

3.3. Окисление углеводородов пероксидом водорода

3.4. Окисление углеводородов периодатом натрия

3.5. Окисление этилбензола Ог

3.6. Исследование методом газовой хромато-масс-спектрометрии (ГХ-МС)

3.7. Исследование окисления порфирина железа методом ЭПР

3.8. Исследование окисления порфиринов железа и марганца методом электронной спектроскопии поглощения

3.9. Исследование окисления порфиринов железа и марганца методом масс-спектрометрии

Выводы

Литература

Рекомендованный список диссертаций по специальности «Химия элементоорганических соединений», 02.00.08 шифр ВАК

Введение диссертации (часть автореферата) на тему «Активность порфиринов металлов, содержащих антиоксидантные 2,6-ди-трет-бутилфенольные заместители, в процессе окисления углеводородов»

ВВЕДЕНИЕ

Порфирины входят в состав большого числа биохимических систем, их синтетические аналоги применяются в фармакологии и медицине. Так, например, РкоШап, Рко^кет используются в фотодинамической терапии опухолевых заболеваний; синтетические порфирины железа и марганца {АЕОЬ 10150) как миметики супероксиддисмутазы проходят клинические испытания в качестве препаратов для борьбы с окислительным стрессом. Липофильные свойства свободных оснований порфиринов и их комплексов с различными металлами обеспечивают накопление этих соединений в липидном бислое клеточных мембран и транспорт в клетки живых организмов.

Однако структурное и функциональное сходство синтетических металлопорфиринов с активными центрами гемовых оксигеназ обусловливает их каталитическую активность в реакциях окисления органических субстратов. В результате, использование порфиринов, например, в качестве сенсибилизаторов в терапии и диагностике опухолевых заболеваний осложняется неконтролируемыми побочными процессами окисления важных биологических субстратов - компонентов белков, ДНК и липидов. В связи с этим возникает необходимость создания новых синтетических порфиринов с управляемой оксигеназной активностью. Данная задача может быть решена в результате получения полифункциональных систем, в которых органическое лигандное окружение металла обеспечивает анти- или прооксидантное действие порфиринов металлов. К таким системам относятся порфирины, содержащие в качестве периферийных органических заместителей антиоксидантные фрагменты 2,6-диалкилфенолов.

Целью работы является направленный синтез порфиринов переходных металлов (Ре111, Мпш, Со", Си11), содержащих в .мезо-положениях макрокольца группы 2,6-ди-т/?ега-бутилфенола, их иммобилизация на матрицу силикагеля

для моделирования связывания активного центра аналога тема с белком и изучение их активности как гомогенных или гетерогенных катализаторов в окислительных процессах.

В задачи работы входило: (1) получение биомиметических полифункциональных систем, в состав молекул которых входят как каталитически активные центры порфирина металла, так и антиоксидантные 2,6-ди-трега-бутилфенольные группы; (2) получение иммобилизованных на матрицу силикагеля порфиринов Бе111, Мпи|, Со11, Си11 с фенольными группами; (3) изучение их каталитической активности в процессах окисления, оксигенирования, эпоксидирования модельных органических субстратов; (4) установление роли фенольных групп в механизме действия данных порфиринов металлов в процессе окисления субстратов, а также влияния на направление процесса.

В работе использованы методы электронной спектроскопии поглощения, инфракрасной спектроскопии, спектроскопии ядерного магнитного резонанса, ЭПР, газовой хроматографии с масс-детектированием и масс-спектрометрии.

Полученные результаты могут быть использованы для формирования новых подходов к созданию нетривиальных про- и антиоксидантов на основе порфиринов металлов, содержащих пространственно-затрудненные фенолы, с переменным эффектом действия.

Работа выполнена при поддержке РФФИ (гранты 06-03-32773, 09-0300090) и Российско-Греческой межгосударственной Программы «Биоматериалы».

Похожие диссертационные работы по специальности «Химия элементоорганических соединений», 02.00.08 шифр ВАК

Заключение диссертации по теме «Химия элементоорганических соединений», Герасимова, Ольга Алексеевна

выводы

1. Впервые получены порфирины металлов (ЯдРМ и РЬ4РМ; М = Ре, Мп, Со, Си) с антноксидантными 2,6-ди-трега-бутилфенольными группами или фенильными заместителями, иммобилизованные на матрице силикагеля с элементоорганическими спейсерами на основе имидазола.

2. Проведено сравнительное исследование активности неиммобилизованных и иммобилизованных на поверхности силикагеля порфиринов металлов (Ре, Мп, Со, Си) в процессах окисления, оксигенирования, эпоксидирования модельных углеводородов (алканов и алкенов) различными окислителями (№Ю4, Н202 и 02).

3. Выявлена зависимость окислительной активности порфиринов металлов от природы металла; природы арильных заместителей в порфириновом макрокольце (фенольная или фенильная группа); длины цепи спейсера и природы окислителя.

4. С использованием методов электронной спектроскопии поглощения, масс-спектрометрии, ЭПР и анализа продуктов реакции изучен механизм окисления углеводородов периодатом натрия в присутствии порфиринов Ре и Мп с 2,6-ди-трет-бутилфенольными группами и установлены активные интермедиаты.

5. Показано образование л-катион-радикала оксокомплекса К4Р'+Ре1У=0, ответственного за механизм действия порфирина железа, и оксокомплекса ^РМп =0, ответственного за механизм действия порфирина марганца.

6. Впервые показана принципиальная возможность управления оксигеназной активностью порфиринов путем введение антиоксидантных 2,6-ди-трет-бутилфенольных групп: для порфирина железа наблюдается усиление, а для порфирина марганца - снижение активности.

Список литературы диссертационного исследования кандидат химических наук Герасимова, Ольга Алексеевна, 2013 год

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