Ковалентно связанная диада на основе фталоцианина цинка и метилфеофорбида а: синтез и физико-химические исследования

И. О. Балашова,^a А. Ю. Толбин,^a П. А. Тараканов,^a А. Р. Крот,^b К. В. Федорова,^b И. А. Сергеева,^b С. А. Трашин,^a,c К. Де Ваэль,^c В. Е. Пушкарев,^a@ М. О. Койфман,^d Г. В. Пономарев^e

^aИнститут физиологически активных веществ РАН, 142432 Черноголовка, Россия

^bМосковский государственный университет имени М.В. Ломоносова, Физический факультет, 119991 Москва, Россия

^cИсследовательская группа AXES, Университет Антверпена, Химический факультет, 2020 Антверпен, Бельгия

^dИнститут макрогетероциклических соединений, Ивановский государственный химико-технологический университет, 153000 Иваново, Россия

^eИнститут биомедицинской химии имени В.Н. Ореховича, 119121 Москва, Россия

^@E-mail: pushkarev@ipac.ac.ru

DOI: 10.6060/mhc210338p

Макрогетероциклы 2021 14(1) 40-50

Посвящается памяти профессора Ларисы Годвиговны Томиловой

Впервые синтезирован ковалентный конъюгат на основе металлофталоцианина и производного хлорина е₆
путем переэтерификации α-кетометилового эфирного фрагмента метилфеофорбида а 2‑(2‑гидроксиметилбензилокси)-9(10),16(17),23(24)-три-трет-бутилфталоцианинатом цинка(II) в мягких условиях. Диада проявляет панхроматическую природу, её ЭСП содержит характерные полосы фталоцианинового и феофорбидного хромофоров. Данные ¹Н ЯМР спектроскопии в совокупности с теоретическими расчетами говорят о наличии пространственных внутримолекулярных взаимодействий между фталоцианиновым, феофорбидным и спейсерным фрагментами диады, позволяя прогнозировать выраженные нелинейно-оптические свойства, а также характерный перенос энергии от возбужденной субъединицы феофорбида к фталоцианиновому ядру. При возбуждении в видимом диапазоне конъюгат демонстрирует красную флуоресценцию с максимумом при 686 нм, близким к максимуму исходного фталоцианината цинка. Более того, диада эффективно генерирует синглетный кислород и в присутствии поливинилпирролидона (ПВП) в качестве биосовместимого солюбилизатора формирует в физиологическом растворе стабильные мицеллы размером от 40 до 100 нм. Данные наночастицы можно рассматривать в качестве перспективного фотосенсибилизатора третьего поколения для тераностики.

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Ковалентно связанная диада на основе фталоцианина цинка и метилфеофорбида а: синтез и физико-химические исследования

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