Физиологическая адаптация нового RuMP штамма факультативных метилотрофных бактерий Brevibacterium methylicum к тяжелой воде

БИОТЕХНОЛОГИЯ

Физиологическая адаптация нового RuMP штамма факультативных
метилотрофных бактерий Brevibacterium methylicum к тяжелой воде

@ 2006 О. В. МОСИН

Московская государственная академия тонкой химической технологии им.
М.В. Ломоносова, 117571, Москва, просп. Вернадского, 86.

Разработан метод физиологической адаптации нового
фенилаланин-продуцирующего RuMP штамма факультативных метилотрофных
бактерий Brevibacterium methylicum к максимальным (98 об.%)
концентрациям 2Н2О с целью последующего микробиологического синтеза
2Н-меченого фенилаланина. Метод заключается в последовательном рассеве
штамма на агаризованных средах М9 с 2 об.% [U -2Н] MetOH со ступенчато
возрастающим градиентом концентрации 2Н2O (от 0 до 98 об.% 2Н2О) и
последующей селекцией колоний по признаку устойчивости к 2Н2О. В
результате применения разработанного подхода для данного штамма
метилотрофных бактерий на среде с 98 об.% 2H2О были отобраны отдельные
колонии, сохранившие высокие ростовые и биосинтетические параметры. За
счет использования адаптированного штамма можно получить 0.95 грамм
2Н-меченого фенилаланина с 1 литра ростовой среды. Показано, что наряду
с фенилаланином штамм синтезирует и выделяет в ростовую среду в
количестве 5-6 ммоль метаболически связанные с ним аминокислоты: аланин,
валин и лейцин/изолейцин. Согласно данным метода масс-спектрометрии EI
MS метиловых эфиров N-диметиламинонафталин-5-сульфонильных (Dns)
производных аминокислот, 2Н-меченые аминокислоты, полученные
микробиологическим синтезом представляли собой смеси молекул с различным
количеством включенных атомов дейтерия; уровень дейтерированности
молекул определяли из масс-спектров по наиболее распространенному пику
молекулярного иона (M)+ каждой аминокислоты – для фенилаланина уровень
дейтерированности составил 6; для аланина -3.1; для валина -4.7; для
лейцина/изолейцина – 5.1 атома дейтерия.

ВВЕДЕНИЕ

В настоящее время микробиологический синтез 2Н-меченых аминокислот
привлекает все большее внимание исследователей вследствие исключительно
природной конфигурации синтезируемых соединений, возможностью
униформного введения дейтериевой метки в молекулы аминокислот и их
низкой стоимости по сравнению с химически синтезированными аналогами [1,
2]. Именно поэтому поиск новых штаммов-продуцентов 2Н-меченых
аминокислот, устойчивых к высоким концентрациям дейтерия в ростовых
средах для их дальнейшего микробиологического использования является
актуальной задачей для современной микробиологической промышленности.

С развитием новых биотехнологических подходов появилась возможность
использовать для направленного синтеза 2Н-меченых аминокислот
биологическую конверсию [U- 2H]MetOH в клетках полученных за счет
мутагенеза и генной инженерии штаммов метилотрофных бактерий,
ассимилирующих MetOH в качестве источника углерода и энергии по
рибулозомонофосфатному (RuMP) или сериновому пути ассимиляции углерода
[3]. Продуктивность метилотрофных бактерий, измеренная по уровню
конверсии MetOH в клеточные компоненты достигает 50%, что делает их
удобными объектами для получения с их помощью 2Н-меченых аминокислот
[4]. Традиционным подходом при этом остаётся выращивание метилотрофных
штаммов-продуцентов аминокислот на минеральных средах с [U- 2Н]MetOH и
максимальными концентрациями 2Н2О [5]. Однако подобные процессы пока не
находят широкого применения в микробиологической промышленности,
вследствие значительного негативного биостатического эффекта,
оказываемого 75-80 об.% 2Н2О на рост многих метилотрофов [6], в то время
как растительные клетки могут нормально развиваться при концентрациях не
более 50 об.% 2H2О [7], а клетки животных не более 35 об.% 2H2О [8]. Как
было показано нами раннее, частично снизить негативный биостатический
эффект 2Н2О у метилотрофов позволяет предварительная клеточная адаптация
к 2Н2О и последующее использование для микробиологического синтеза
2Н-меченых аминокислот адаптированных форм метилотрофных бактерий [9].
Явление клеточной адаптации к 2H2О интересно не только само по себе, но
оно также позволяет получать уникальный биологический материал, несущий
дейтериевую метку, очень удобный для разнопрофильных микробиологических
исследований. В соответствиие с этим, целью настоящей работы было
исследование процесса физиологической адаптации нового
фенилаланин-продуцирующего RuMP штамма факультативных метилотрофных
бактерий Brevibacterium methylicum к максимальным (98% об.)
концентрациям 2Н2О в ростовой среде. Поскольку биосинтетический
потенциал данного метилотрофного штамма при росте на 2Н2О к началу
проведения работы был изучен недостаточно, представляло интерес
исследование его способности к микробиологическому синтезу 2Н-меченого
фенилаланина и других аминокислот в условиях максимально насыщенной
дейтерием среды.

ОБЪЕКТ ИССЛЕДОВАНИЯ И МЕТОДЫ

Объектом исследования служил полученный за счет мутагенеза
нитрозогуанидином лейцинзависимый грам-положительный штамм RuMP
факультативных метилотрофных бактерий Brevibacterium methylicum ВКПМ В
5652, продуцент фенилаланина [10]. Потребость штамма в лейцине
составляет 10 мг/л. Родительский штамм был получен из Всероссийской
коллекции промышленных микроорганизмов (ВКПМ) Государственного
научно-исследовательского центра генетики и селекции промышленных
микроорганизмов ГНИИГЕНЕТИКА.

Для приготовления ростовых сред и адаптации штамма использовали 2H2O
(99.9 ат.% 2H) и [U- 2Н] MetOH (97.5 ат.% 2H), полученные из Российского
научно-исследовательского центра ИЗОТОП (Санкт-Петербург, РФ). Для
создания высокого градиента концентрации 2Н2О в ростовых средах
использовали 2Н2О с атомным содержанием дейтерия 99.9%. Фосфатсодержащие
соли были дважды перекристаллизованы в абсолютной 2Н2О перед их
использованием и высушены в вакууме. Тем не менее, процент
дейтерированности ростовых сред после стериллизации влажным паром,
измеренный методом ЯМР был ниже на 8-10% изотопной чистоты исходной
2Н2О). По необходимости 2H2O очищали от вредных примесей, перегоняя её
над перманганатом калия [11].

Выращивание штамма проводили в минеральной среде M9 [12], приготовленой
на основе различных концентраций 2Н2О (см. таблицу) с добавками
протонированного лейцина и [U-2H] MetOH при 370 С в колбах Эрленмейера
вместимостью 250 мл с наполнением средой до 50 мл в условиях интенсивной
аэрации по методике [13]. После 6-7 суток роста клетки отделяли
центрифугированием (10000 об/мин, 20 мин). В культуральной жидкости
анализировали секретируемые аминокислоты.

Адаптацию штамма к 2Н2О проводили на агаризованных средах М9 (2%-ный
агар), содержащих ступенчато возрастающий градиент 2Н2О (от 0 вплоть до
98 об.% 2Н2О). При этом использовали последовательный рассев штамма до
отдельных колоний и последующую селекцию колоний, выросших на средах со
ступенчатом градиентом 2Н2О. Отобранный штамм хранили в 50%-ном растворе
(в 2Н2О) глицерина при -140С.

Морфологию клеток исследовали с помощью
интерференционно-поляризационного микроскопа МБР-5 (Венгрия).

Бактериальный рост оценивали по величине оптической плотности суспензии
клеток, измеренной на спектрофотометре Beckman-DU6 (США) при 540 нм в
кварцевой кювете с длиной оптического пути 10 мм.

Тонкослойную хроматографию (ТСХ) аминокислот проводили на пластинках
Silufol UV-254 (Чехо-Словакия) в системе растворителей: изо-PrOH-аммиак,
(7:3).

Секретируемый фенилаланин определяли на приборе Beckman DU-6 (США) при
540 нм в образцах культуральной жидкости, объёмом 10 мкл после ее
обработки 0.1% раствором нингидрина в ацетоне.

Уровни включения дейтерия в молекулы аминокислот определяли методом
масс-спектрометрии EI MS в виде метиловых эфиров N-Dns-производных
аминокислот на приборе MB-80A (Hitachi, Япония) при ионизирующем
напряжении 70эВ, используя прямую дериватизацию лиофилизированных
культуральных жидкостей дансилхлоридом и диазометаном [14].

РЕЗУЛЬТАТЫ И ОБСУЖДЕНИЕ

Выращивание штамма на 2Н2О-содержащих средах.

Для выращивания штамма был выбран ступенчато-увеличивающийся градиент
концентрации 2H2О в ростовых средах в присутствии 2 об.% [U -2H] MetOH,
так как предпологалось, что постепенное привыкание клетки к 2Н2О будет
оказывать благоприятный эффект на параметры роста и общее самочувствие
культуры (таблица). Для компенсации ауксотрофности по лейцину эту
аминокислоту добавляли в ростовую среду в протонированном виде в
концентрации 10 мг/л. Сначала исходный штамм выращивали на
2Н2О-содержащих средах без его предварительной адаптации к 2Н2О, для
того чтобы определить его ростовые и биосинтетические параметры на этих
средах. При росте исходного штамма на контрольной среде с обычной водой
продолжительность лаг-фазы и время клеточной генерации составили 20 и
2.2 ч соответственно (таблица, опыт 1). В промежуточных экспериментах
эти параметры изменялись пропорционально концентрации 2Н2О. В частности,
продолжительность лаг-фазы и время клеточной генерации увеличивались, а
рост и уровень накопления фенилаланина уменьшались, причем самые низкие
значения были зафиксированы на максимально дейтерированной среде с 98
об.% 2Н2О. Так, в эксперименте (5), таблица, выход микробной биомассы
был снижен в 3.3, а уровень накопления фенилаланина в ростовой среде в
2.7 раз по сравнению с контролем, поэтому было необходимо проводить
адаптацию штамма к 2Н2О.

Таблица. Изотопный состав ростовых сред и параметры бактериального роста
исходного штамма

Компоненты среды, об.%

H2O 2H2O MetOH [U -2H]

MetOHлаг-фаза

(ч)Выход биомассы((%) Время генерации

(ч)Максимальный уровень накопления фенилаланина в ростовой среде

(%)
(1)9802020100.02.2100.0(2)73.524.5023485.92.697.1(3)49.049.0024460.53.29
8.8(4)24.573.5024947.23.887.6(5)098.0026030.14.937.0

Клеточная адаптация к 2Н2О.

Специальный подход по адаптации заключался в серии из четырех
адаптационных пассажей исходной культуры на твёрдых агаризованных средах
с 2 об.% [U-2H] MetOH с 0, 24.5, 49, 73.5 и 98 об.% 2Н2О. При этом
отбирали отдельные колонии, выросшие на средах с низкими концентрациями
2Н2О. Затем их последовательно пересевали на среды с большей
концентрацией 2Н2О, включая среду с 98 об.% 2H2О, проводя их
параллельные контрольные рассевы на протонированной среде (степень
выживаемости бактерий составила не более 40%).

За ходом адаптации следили по изменениям продолжительности лаг-фазы,
времени клеточной генерации и выходов микробной биомассы, а также по
максимальному уровню накопления фенилаланина в ростовой среде (рис. 2).
Так, выход микробной биомассы, время клеточной генерации и уровень
накопления фенилаланина в ростовой среде при росте адаптированного к
2Н2О штамма в 98 об.% 2Н2О изменяются по сравнению с контрольными
условиями на 13, .. и 5%, т. е. незначительно (рис. 2, опыт 5’).
Продолжительность времени генерации существенно не отличается от
исходного штамма на Н2О-среде. Адаптированные к 2Н2О клетки сохранили
способность синтезировать и экзогенно продуцировать фенилаланин в
ростовую среду, который можно выделять в количестве 0.95 г/л.

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Рис.1

Изучение продукции фенилаланина на 2Н2О-содержащих средах.

Во всех экспериментах не зависимо от присутствия 2Н2О в ростовой среде
было зафиксировано увеличение продукции фенилаланина на ранней фазе
экспоненциального роста, когда выход микробной биомассы был
незначителен, в то время как на фазе позднего экспоненциального роста
наблюдалось снижение уровня его накопления в ростовой среде (рис. 3).
Для того чтобы объяснить эффект снижения уровня накопления фенилаланина
были высказаны возможные предположения о морфологической неоднородности
микробной популяции, ингибировании биосинтеза фенилаланина конечным
продуктом нарушении транспорта фенилаланина через клеточную мембрану.
Результаты по микроскопическому исследованию растущей популяции
микроорганизмов показали, что данный характер динамики накопления
фенилаланина не коррелировал с качественными изменениями клеточной
морфологии на поздних стадиях роста, что служило подтверждением
морфологической однородности микробной популяции. Скорее всего,
накопленный экзогенно в процессе роста фенилаланин ингибировал ферменты
собственного пути биосинтеза. Кроме того, не исключена возможность, что
при выращивании без рН-статирования может происходить как обратное
превращение секретируемого фенилаланина в интермедиаторные соединения
его биосинтеза по пути шикимовой кислоты, так и спонтанная ассимиляция
фенилаланина клеткой для обеспечения своих собственных метаболических
потребностей, что отмечено в других работах [15, 16]. Эффект уменьшения
уровня накопления фенилаланина наблюдался при росте как на
протонированной, так и на среде с 98 об.% 2Н2О, что затрудняло его
исследование (рис. 3). Из-за того, что на среде с 98 об.% 2Н2О
ухучшались все ростовые параметры, было сделано предположение, что
уменьшение уровня накопления фенилаланина в ростовой среде относится не
к изменению транспорта фенилаланина через клеточную мембрану, а к
негативному биостатическому эффекту 2Н2О. Данные по исследованию
культуральной жидкости методом ТСХ показали, что кроме фенилаланина
данный штамм синтезирует и накапливает в ростовой среде незначительные
количества (на уровне 5-6 ммоль) метаболически связанных с ним
аминокислот (аланин, валин, лейцин/изолейцин), присутствие которых также
подтверждалось анализом смеси метиловых эфиров N-DNS-производных
аминокислот методом масс-спектрометрии EI MS.

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00002701ffff030000000000

Рис.2.

Изучение уровней включения дейтерия в молекулы аминокислот.

В настоящей работе уровни включения дейтерия в молекулы аминокислот
определяли методом масс-спектрометрии EI MS в виде метиловых эфиров
N-Dns-производных аминокислот, за счет сопоставления молекулярных масс
протонированных и 2Н-меченых производных аминокислот.

Полученные микробиологическим синтезом 2Н-меченые аминокислоты
представляли собой смеси изотопнозамещённых форм молекул, различающихся
количеством атомов водорода, замещённых на дейтерий. Вследствие этого
эффекта пики молекулярных ионов метиловых эфиров N-Dns-аминокислот в
масс-спектрах были полиморфно расщеплены на кластеры за счет примеси
молекул с отношениями m/z, больше или меньше детектируемых прибором
величин (М)+ с различным вкладом в суммарный уровень дейтерированности.
В качестве примера на рис. 4, б приведен масс-спектр смеси метиловых
эфиров N-Dns-производных аминокислот полученных со среды с 98 об.% 2Н2О
(масс-спектр приведен относительно контрольных условий (а) на обычной
воде). Подсчет уровня дейтерированности молекул аминокислот проводили по
величине самого интенсивного пика молекулярного иона (М)+,
зарегистрированного самим масс-спектрометром; для фенилаланина – шесть
(М+ при m/z 418 вместо М+ при m/z 412 для протонированного метилового
эфира N-Dns-фенилаланина), для аланина -3.1 (М+ при m/z 339.5 вместо М+
при m/z 336.4), для валина -4.7 (М+ при m/z 369.2 вместо М+ при m/z
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и действия 2H2О как растворителя (большая структурированность, плотность
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