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With only 2 exceptions, most of the 10-11 different types of nitroge-nase substrates known so far are small molecules with terminal triple-bonds, or cyclopropenc-type quasi triple bond. From the known nitrogenase-cata!yzed reactions of these substrates and their relative coordination affinities at nitrogenase active-center, it has been inferred by us[1] that these substrate moleciles arc most probably coordinated jn similar μ3(η2) modes at nitrogenase active-center, and a twin-sited dicubane-cluster structural...

With only 2 exceptions, most of the 10-11 different types of nitroge-nase substrates known so far are small molecules with terminal triple-bonds, or cyclopropenc-type quasi triple bond. From the known nitrogenase-cata!yzed reactions of these substrates and their relative coordination affinities at nitrogenase active-center, it has been inferred by us[1] that these substrate moleciles arc most probably coordinated jn similar μ3(η2) modes at nitrogenase active-center, and a twin-sited dicubane-cluster structural model of active-center has been proposed. It has also been pointed out[1] that, for those substrate molecules with triple-bonds but without "tail", namely, cyciopro-pene, N=N, C=N-, and HC≡CH, both the donble-end-on-plus-single-side-on mode and the singie-end-on- plus-double-ride-on-mode of μ3(η2) coordination are compatible with the same trimiclear active-center(lMo-Fe) . In the present work, results of approsimate quantum-chemical EHMO calculations and qualitative molecular orbital discussions are presented, which show that in the case of cyclopropene, the double-end-on (pseudo) -plus-single side-on mode of μ3(η2) coordination is energetically far more favorable than the alternative mode of μ3(η2) coordination; in the case of N≡N and HN≡C (hypothetical iso-hydrocyaixic acid), the double-end-on -plus-single-side-on mode of μ3(η2) coordination are also energetically more favorable than the alternative mode of μ3(η2) coordination; this is still true in the case of HC≡CH, but here the difference in coordination bond energies for the 2 modes of μ3(η2) coordination is rather small. These results arc in agreement with the known esperimental fact that cyclopropene is a nirrogenase substrate and a strang competitive inhibitor of nitrogenase-catalyzel reductionof N≡N, and that both modes of μ3(η2) coordination are known for acetylenes in their transition-metal cluster complexes. The double-end-on(pseu.lo)-plus-single-side-on coordination of cyclopene and of N≡N at the trinuclear attive-c-nter also provides satisfactory interpretation of the structural selectivity of the njtrogenase catalyzed reduction products of cyclopropene, and the transition state configuration of the D2+2H++ 2e-→2HD reaction specifically catalyzed by nitrogenase in the presence of N2.

迄今所知的固氮酶十来种底物中,除极少数例外,大多数都是末端具有三重键(或环丙烯型的准三重键)的小分子。从这些底物的已知酶促反应和在固氨酶活性中心的相对配位亲合力,我们曾推断这些底物分子很可能是以相同的μ_3(η~2)型方式络合在固氮酶活性中心上的,并在此基础上提出了并联双座双立方烷型原子簇结构的活性中心模型。同时指出,对于那些末端有三重键但无“尾巴”的底物分子,如N≡N,C≡N~-,和HC≡CH,在三核活性中心(1Mo—2Fe)进行μ_3(η~2)型络合,有两种可能的方式即双端基加单侧基型络合和单端基加双侧基络合。本文报导了EHMO近似计算和定性的分子轨道讨论结果。结果表明:在环丙烯情况下,双(准)端基加单侧基型络合比单(准)端基加双侧基型络合在能量上要有利得多,而且它的络合键能相当大;在N≡N和HN≡C(假想的异氢腈酸)情况下,双端基(或准端基)加单侧基型络合比单端基加双侧基型络合在能量上亦较为有利;乙炔的情况也是这样,但两种络合方式的络合键能之差比较小。这些结果与下述的实验事实是一致的:环丙烯是固氮酶的底物,而且是N≡N酶促还原加氢的强竞争性抑制剂;两种按μ_3(η~2)型方式络合的炔烃过渡金属原子簇络合...

迄今所知的固氮酶十来种底物中,除极少数例外,大多数都是末端具有三重键(或环丙烯型的准三重键)的小分子。从这些底物的已知酶促反应和在固氨酶活性中心的相对配位亲合力,我们曾推断这些底物分子很可能是以相同的μ_3(η~2)型方式络合在固氮酶活性中心上的,并在此基础上提出了并联双座双立方烷型原子簇结构的活性中心模型。同时指出,对于那些末端有三重键但无“尾巴”的底物分子,如N≡N,C≡N~-,和HC≡CH,在三核活性中心(1Mo—2Fe)进行μ_3(η~2)型络合,有两种可能的方式即双端基加单侧基型络合和单端基加双侧基络合。本文报导了EHMO近似计算和定性的分子轨道讨论结果。结果表明:在环丙烯情况下,双(准)端基加单侧基型络合比单(准)端基加双侧基型络合在能量上要有利得多,而且它的络合键能相当大;在N≡N和HN≡C(假想的异氢腈酸)情况下,双端基(或准端基)加单侧基型络合比单端基加双侧基型络合在能量上亦较为有利;乙炔的情况也是这样,但两种络合方式的络合键能之差比较小。这些结果与下述的实验事实是一致的:环丙烯是固氮酶的底物,而且是N≡N酶促还原加氢的强竞争性抑制剂;两种按μ_3(η~2)型方式络合的炔烃过渡金属原子簇络合物都已发现。环丙烯和N≡N在三核活性中心的双端基(或准端基)加单侧基型络合也能较

After administration of β-ecdysone at the early stage (during 0-6 hours) to fifth instar larvae of Bombyx mori L. reared on mulberry leaves or semisynthetic diet, the duration of the last instar was not shortened but rather prolonged to 8-9 hours, the weights of silkgland and cocoon shell were increased about 10% and 5-8% respectively. The activities of the transaminases for glycine and alanine formation such as 1-alanine-glyoxylate transaminase, 1-alanine-ketomalonate transaminase and ornithine-6 transami-nase...

After administration of β-ecdysone at the early stage (during 0-6 hours) to fifth instar larvae of Bombyx mori L. reared on mulberry leaves or semisynthetic diet, the duration of the last instar was not shortened but rather prolonged to 8-9 hours, the weights of silkgland and cocoon shell were increased about 10% and 5-8% respectively. The activities of the transaminases for glycine and alanine formation such as 1-alanine-glyoxylate transaminase, 1-alanine-ketomalonate transaminase and ornithine-6 transami-nase in the cells of posterior division of the silkgland and of the fat body were markedly increased as compared with that of the controls.While oral injection of β-ecdysone at a later stage (just before larval maturation) shortened the duration of the last instar by 12--18 hours, the activities of 1-alanine-glyoxylate transaminase, 1-alanine-ketomalonate transaminase in cells of the posterior division of the silkgland and of the fat body also increased rapidly as compared with that of the controls.The mechanism of action of 3-ecdysone and juvenile hormone and the relationship between these two insect hormones in regulating the amino acids metabolism and the biosynthesis of silk fibroin are discussed.

本文研究了植源性β-蜕皮素(简称MH)对家蚕丝腺成长及合成甘氨酸、丙氨酸有关酶系的影响,探讨了5龄不同时期添食β-蜕皮素后丝腺体的成长及后部丝腺和脂肪体中丙氨酸-酮丙二酸、丙氨酸-乙醛酸和鸟氨酸转氨酶活力的变化。通过实验观察到:(1)5龄早期(饷食)添食β-蜕皮素,龄期延长8—9小时,茧层量增加,后部丝腺和脂肪体内丙氨酸-酮丙二酸转氨酶、丙氨酸-乙醛酸转氨酶在处理后6-12小时内,比对照组增高40—50%。随之酶活力略下降,至5龄后期复又升高,明显超过对照组。脂肪体中鸟氨酸转氨酶在β-蜕皮素处理后6小时和48小时均低于对照组。12—24小时以及48小时后直至老熟则明显高于对照组。(2)5龄后期(V—136小时)口腔注射β-蜕皮素,龄期缩短12—18小时。脂肪体和丝腺体中丙氨酸-酮丙二酸转氨酶、丙氨酸-乙醛酸转氨酶活力明显高于对照组(一般增高20—40%),老熟时迅速下降。本文对有关保幼激素和β-蜕皮素对5龄家蚕两种靶细胞(丝腺细胞和脂肪细胞)的相互配合和制约以完成对蚕整体的调节控制,以及这两种昆虫激素应用于蚕业生产以控制5龄期的长短和增加蚕丝产量等方面进行了讨论。

In insects tyrosine transamination and polyphenol oxidation play an importantrole in the catabolism of tyrosine.There are two main pathways for the catabolismof tyrosine:one is to form p-hydroxyphenylpyruvate by tyrosine transaminase,theother is to form dopa and then sclerotin by polyphenoloxidase.Dopa can also becatabolized to melanin by polyphenoloxidase.In the present paper,it was demonstrated that after applying adequate doses ofthe juvenile hormone analogue ZR-515 and β-ecdysone into 4th instar and 5th...

In insects tyrosine transamination and polyphenol oxidation play an importantrole in the catabolism of tyrosine.There are two main pathways for the catabolismof tyrosine:one is to form p-hydroxyphenylpyruvate by tyrosine transaminase,theother is to form dopa and then sclerotin by polyphenoloxidase.Dopa can also becatabolized to melanin by polyphenoloxidase.In the present paper,it was demonstrated that after applying adequate doses ofthe juvenile hormone analogue ZR-515 and β-ecdysone into 4th instar and 5th instarlarvae,and larvae during ecdysis to the 5th instar,the activities of tyrosine transami-nase and polyphenoloxidase were increased at various stages as compared with thecontrol in the development of Philosamia cynthia ricini.It was shown that the tyro-sine transaminase and polyphenoloxidase were regulated by these two insect hormones.But under certain rare circumstances no induction of tyrosine transaminase andpolyphenoloxidase was observed upon application of juvenile hormone analogue or β-ecdysone.This may be due to the high level of these hormones already present or toother unknown factors.

本文报道了鳞翅目天蚕蛾科蓖麻蚕的酪氨酸转氨酶和多酚氧化酶的变化以及昆虫激素对这两个酶的调节控制。作者观察到蓖麻蚕自四龄眠至五龄后期的活力有明显的变化规律,保幼激素类似物ZR-515和β-蜕皮素对该酶有诱导作用。此外,我们还观察到四龄眠期和五龄期间保幼激素类似物ZR-515和β-蜕皮素对多酚氧化酶也有明显的调节控制作用。

 
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