Isolation and structural determination of C8-vinyl-bacteriochlorophyll d from the bciA and bchU double mutant of the green sulfur bacterium Chlorobaculum tepidum

Isolation and structural determination of C8-vinyl-bacteriochlorophyll d from the bciA and bchU double mutant of the green sulfur bacterium Chlorobaculum tepidum
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绿硫细菌温热绿杆菌 bciA 和 bchU 双突变体中 C8-乙烯基细菌叶绿素 d 的分离和结构测定

DOI:
10.1007/s11120-014-0007-7
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发表时间:
2014
期刊:
Photosynth. Res.
影响因子:
--
通讯作者:
H. Tamiaki
H. Tamiaki
中科院分区:
--
文献类型:
--
作者:
J. Harada;T. Mizoguchi;K. Nomura;H. Tamiaki

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构建了绿色硫细菌Chlorobaculum tepidum的BciA和BchU缺失突变体,该突变体分别催化细菌叶绿素(BChl)c的C8-乙烯基还原和C20位甲基化。该突变体积累了C8-乙烯基-BChld衍生物,并通过NMR、质谱、圆二色谱以及化学修饰充分表征了主要色素的分子结构:(31 R)-8-乙烯基-12-乙基-(R[V,E])BChld被证实为细胞中的一种新的BChld。该色素在体外胶束溶液中形成了类似于叶绿体的自聚集体,其形成速度比绿色硫细菌小绿杆菌NCIB 8327 d合成BChld同系物的(31 R)-8,12-二乙基-(R[E,E])BChld的形成速度快。它们的Qy红移吸收带在761 nm处几乎相同,其值大于R[E,E]BChlc和R[V,E]BChlc体外自聚集体的Qy值(737 nm)和Qy值(726 nm),而前者的单体态Qy吸收带在较短的波长处。两种BChld分子的自聚集红移为110 nm,远大于BChlsc分子的红移([E,E]为75 nm,[V,E]为64 nm)。
The mutant lacking enzymes BciA and BchU, that catalyzed reduction of the C8-vinyl group and methylation at the C20 position of bacteriochlorophyll (BChl)c, respectively, in the green sulfur bacteriumChlorobaculum tepidum, were constructed. This mutant accumulated C8-vinyl-BChldderivatives, and a molecular structure of the major pigment was fully characterized by its NMR, mass, and circular dichroism spectra, as well as by chemical modification: (31R)-8-vinyl-12-ethyl-(R[V,E])BChldwas confirmed as a new BChldspecies in the cells. In vitro chlorosome-like self-aggregates of this pigment were prepared in an aqueous micellar solution, and formed more rapidly than those of (31R)-8,12-diethyl-(R[E,E])BChldisolated from the green sulfur bacteriumChlorobaculum parvumNCIB8327d synthesizing BChldhomologs. Their red-shiftedQyabsorption bands were almost the same at 761 nm, and the value was larger than those of in vitro self-aggregates of R[E,E]BChlc(737 nm) and R[V,E]BChlc(726 nm), while the monomeric states of the former gaveQybands at shorter wavelengths than those of the latter. Red shifts by self-aggregation of the two BChldspecies were estimated to be 110 nm and much larger than those by BChlsc(75 nm for [E,E] and 64 nm for [V,E]).
T.Mizoguchi:“来自绿硫细菌 Chlorobium v​​ibrioforme 的一整套细菌叶绿素-d 同系物和差向异构体的分离和结构测定及其在疏水性溶剂中的聚集特性”Photochem.Photobiol.Sci.. 1。
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DOI: --
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