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沙漠蝗Schistocerca gregaria蜕皮甾体生物合成过程中C-22位羟基化的机制。

Mechanism of hydroxylation at C-22 during the biosynthesis of ecdysteroids in the locust Schistocerca gregaria.

作者信息

Greenwood D R, Rees H H

出版信息

Biochem J. 1982 Dec 15;208(3):857-64. doi: 10.1042/bj2080857.

DOI:10.1042/bj2080857
PMID:7165737
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC1154042/
Abstract
  1. The fates of the 22-pro-R and 22-pro-S hydrogen atoms of cholesterol during the biosynthesis of ecdysteroids in the ovaries of Schistocerca gregaria were investigated. 2. Two stereospecifically labelled cholesterol species, obtained by incubating 3R,2R- and 3R,2S-[2-14C, 2-3H]mevalonic acid with rat liver preparations, were administered, in turn, to maturing adult female locusts and the radiolabelled ecdysteroid conjugates isolated from the eggs. Enzymic hydrolysis of the conjugates yielded free ecdysteroids, from which ecdysone was purified. 3. Derivative formation and oxidation at C-22 of both ecdysone samples indicated that the 22-pro-R and 22-pro-S hydrogen atoms of cholesterol were stereospecifically eliminated and retained respectively during ecdysteroid formation. This indicates that C-22 hydroxylation in ecdysone biosynthesis is direct and occurs with retention of configuration.
摘要
  1. 研究了在沙漠蝗卵巢中蜕皮甾体生物合成过程中胆固醇22 - 前R和22 - 前S氢原子的命运。2. 通过将3R,2R - 和3R,2S - [2 - ¹⁴C, 2 - ³H]甲羟戊酸与大鼠肝脏制剂孵育获得的两种立体特异性标记的胆固醇,依次给予成熟的成年雌性蝗虫,并从卵中分离出放射性标记的蜕皮甾体缀合物。缀合物的酶促水解产生游离的蜕皮甾体,从中纯化出蜕皮激素。3. 两种蜕皮激素样品在C - 22处的衍生物形成和氧化表明,在蜕皮甾体形成过程中,胆固醇的22 - 前R和22 - 前S氢原子分别被立体特异性消除和保留。这表明蜕皮激素生物合成中的C - 22羟基化是直接的,并且构型保持不变。

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本文引用的文献

1
20alpha,22x-Dihydroxycholesterol, an intermediate in the biosynthesis of pregnenolone (3beta-hydroxypregn-5-en-20-one) from cholesterol.20α,22α-二羟基胆固醇,是胆固醇生物合成孕烯醇酮(3β-羟基孕-5-烯-20-酮)过程中的一种中间体。
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The biosynthesis of cholesterol from acetate-1-C14 by cellular fractions of rat liver.用大鼠肝脏细胞组分从乙酸-1-C14合成胆固醇
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[On the chemistry of ecdysone. VII. Analysis of the crystal and molecular structure of the molting hormone in insects, ecdysone, using the automized folding molecule method].[关于蜕皮激素的化学。VII. 使用自动折叠分子方法分析昆虫蜕皮激素的晶体和分子结构]
Chem Ber. 1965 Jul;98(7):2403-24. doi: 10.1002/cber.19650980744.
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The stereochemistry of tritium at carbon atoms 1, 7, and 15 in cholesterol derived from (3R,2R)-(2-3H)-mevalonic acid.
J Biol Chem. 1969 Nov 25;244(22):6064-73.
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Sterol biosynthesis.甾醇生物合成
Biochem Soc Symp. 1970;29:45-77.
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The stereochemistry of hydrogen elimination from C-7 during biosynthesis of ecdysones in insects and plants.昆虫和植物中蜕皮激素生物合成过程中C-7位氢消除的立体化学。
Biochem J. 1973 Sep;136(1):135-45. doi: 10.1042/bj1360135.
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Proc R Soc Lond B Biol Sci. 1972 Feb 15;180(1059):167-77. doi: 10.1098/rspb.1972.0012.
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