共查询到20条相似文献,搜索用时 15 毫秒
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碳氢键选择氧化是合成化学领域的重要课题,其中烷烃选择性羟化反应更是面临着化学选择性、区域选择性和立体选择性等多重挑战.细胞色素P450酶广泛分布于动植物和微生物体内,是公认的多功能生物氧化催化剂. P450酶对惰性C—H键的选择性氧化具有独特优势,在催化烷烃选择性羟化反应方面拥有巨大潜力.本综述简述了P450单加氧酶及其催化烷烃选择性羟化的反应机理,梳理了来自CYP153家族、CYP52家族和其他家族的天然P450酶催化各类烷烃底物的氧化反应和选择性,讨论了理性设计和定向进化策略在开发烷烃羟化P450突变酶过程中的经典案例,介绍了底物工程、诱饵分子、双功能小分子协同催化等几种化学活化P450酶的策略及其在烷烃羟化上的应用,探讨了P450酶在烷烃选择性羟化方面所面临的挑战和解决途径,并展望了其应用前景. 相似文献
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Han Dong Meiling Li Ling Jin Xiaorong Xie Mengfei Li Jianhe Wei 《Molecules (Basel, Switzerland)》2022,27(1)
Angelica sinensis, a perennial herb that produces ferulic acid and phthalides for the treatment of cardio-cerebrovascular diseases, prefers growing at an altitude of 1800–3000 m. Geographical models have predicted that high altitude, cool temperature and sunshade play determining roles in geo-authentic formation. Although the roles of altitude and light in yield and quality have been investigated, the role of temperature in regulating growth, metabolites biosynthesis and gene expression is still unclear. In this study, growth characteristics, metabolites contents and related genes expression were investigated by exposing A. sinensis to cooler (15 °C) and normal temperatures (22 °C). The results showed that plant biomass, the contents of ferulic acid and flavonoids and the expression levels of genes related to the biosynthesis of ferulic acid (PAL1, 4CLL4, 4CLL9, C3H, HCT, CCOAMT and CCR) and flavonoids (CHS and CHI) were enhanced at 15 °C compared to 22 °C. The contents of ligustilide and volatile oils exhibited slight increases, while polysaccharide contents decreased in response to cooler temperature. Based on gene expression levels, ferulic acid biosynthesis probably depends on the CCOAMT pathway and not the COMT pathway. It can be concluded that cool temperature enhances plant growth, ferulic acid and flavonoid accumulation but inhibits polysaccharide biosynthesis in A. sinensis. These findings authenticate that cool temperature plays a determining role in the formation of geo-authentic and also provide a strong foundation for regulating metabolites production of A. sinensis. 相似文献
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Jonathan R. Chekan Shaun M. K. McKinnie Malia L. Moore Shane G. Poplawski Todd P. Michael Bradley S. Moore 《Angewandte Chemie (International ed. in English)》2019,58(25):8454-8457
Kainic acid, the flagship member of the kainoid family of natural neurochemicals, is a widely used neuropharmacological agent that helped unravel the key role of ionotropic glutamate receptors, including the kainate receptor, in the central nervous system. Worldwide shortages of this seaweed natural product in the year 2000 prompted numerous chemical syntheses, including scalable preparations with as few as six‐steps. Herein we report the discovery and characterization of the concise two‐enzyme biosynthetic pathway to kainic acid from l ‐glutamic acid and dimethylallyl pyrophosphate in red macroalgae and show that the biosynthetic genes are co‐clustered in genomes of Digenea simplex and Palmaria palmata. Moreover, we applied a key biosynthetic α‐ketoglutarate‐dependent dioxygenase enzyme in a biotransformation methodology to efficiently construct kainic acid on the gram scale. This study establishes both the feasibility of mining seaweed genomes for their biotechnological prowess. 相似文献
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Formation of the Δ18,19 Double Bond and Bis(spiroacetal) in Salinomycin Is Atypically Catalyzed by SlnM,a Methyltransferase‐like Enzyme 下载免费PDF全文
Dr. Chunyan Jiang Zhen Qi Dr. Qianjin Kang Jing Liu Dr. Ming Jiang Prof. Dr. Linquan Bai 《Angewandte Chemie (International ed. in English)》2015,54(31):9097-9100
Salinomycin is a widely used polyether coccidiostat and was recently found to have antitumor activities. However, the mechanism of its biosynthesis remained largely speculative until now. Reported herein is the identification of an unprecedented function of SlnM, homologous to O‐methyltransferases, by correlating its activity with the formation of the Δ18,19 double bond and bis(spiroacetal). Detailed in vivo and in vitro investigations revealed that SlnM, using positively charged S‐adenosylmethionine (SAM) or sinefungin as the cofactor, catalyzed the spirocyclization‐coupled dehydration of C19 in a highly atypical fashion to yield salinomycin. 相似文献
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Liuqing Yang Marco Hill Dr. Meitian Wang Dr. Santosh Panjikar Dr. Joachim Stöckigt Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(28):5211-5213
Cutting carbons : The three‐dimensional structure of polyneuridine aldehyde esterase (PNAE) gives insight into the enzymatic mechanism of the biosynthesis of C9‐ from C10‐monoterpenoid indole alkaloids (see scheme). PNAE is a very substrate‐specific serine esterase. It harbors the catalytic triad S87‐D216‐H244, and is a new member of the α/β‐fold hydrolase superfamily. Its novel function leads to the diversification of alkaloid structures.
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Ⅱ型脂肪酸合成途径(FAS-Ⅱ)是细菌和植物体内进行饱和/不饱和脂肪酸合成的唯一必需途径.FAS-Ⅱ由一系列单一基因编码的可溶性酶组成,通过依次循环式的识别和催化由酰基载体蛋白(ACP)共价携带的脂肪酸碳链底物来实现特定长度饱和/不饱和脂肪酸碳链的延长和合成.由于FAS-Ⅱ在细菌生理活动中具有不可或缺的作用,同时与哺乳动物脂肪酸合成途径FAS-I存在显著差异,FAS-Ⅱ的酶系长久以来都被公认为是重要的抗菌药物靶标群.因此,阐明该途径酶系的催化调控机制,发展靶向FAS-Ⅱ酶系的抗菌药物是该领域的研究重点.综述FAS-Ⅱ近年的分子机制研究和药物发现进展有助于进一步了解FAS-Ⅱ的生物学功能并推动全新抗菌药物的发现. 相似文献
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Dr. Jean-Noël Rebilly Wenli Zhang Dr. Christian Herrero Dr. Hachem Dridi Dr. Katell Sénéchal-David Dr. Régis Guillot Prof. Frédéric Banse 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):659-668
Rieske dioxygenases are metalloenzymes capable of achieving cis-dihydroxylation of aromatics under mild conditions using O2 and a source of electrons. The intermediate responsible for this reactivity is proposed to be a cis-FeV(O)(OH) moiety. Molecular models allow the generation of a FeIII(OOH) species with H2O2, to yield a FeV(O)(OH) species with tetradentate ligands, or {FeIV(O); OH.} pairs with pentadentate ones. We have designed a new pentadentate ligand, mtL42, bearing a labile triazole, to generate an “in-between” situation. Two iron complexes, [(mtL42)FeCl](PF6) and [(mtL42)Fe(OTf)2]), were obtained and their reactivity towards aromatic substrates was studied in the presence of H2O2. Spectroscopic and kinetic studies reflect that triazole is bound at the FeII state, but decoordinates in the FeIII(OOH). The resulting [(mtL42)FeIII(OOH)(MeCN)]2+ then lies on a bifurcated decay pathway (end-on homolytic vs. side-on heterolytic) depending on the addition of aromatic substrate: in the absence of substrate, it is proposed to follow a side-on pathway leading to a putative (N4)FeV(O)(OH), while in the presence of aromatics it switches to an end-on homolytic pathway yielding a {(N5)FeIV(O); OH.} reactive species, through recoordination of triazole. This switch significantly impacts the reaction regioselectivity. 相似文献
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催化光度法测定粉煤灰中微量钍 总被引:2,自引:0,他引:2
在pH2.0的HNO3介质中,痕量钍㈣对过氧化氢氧化苦胺酸偶氮变色酸(PAACA)的褪色反应有强的催化作用。加入乳化剂OP能提高其灵敏度,催化程度与钍(Ⅳ)量线性相关。借此建立了测定痕量钍(Ⅳ)的分光光度法。结果表明:有色溶液的最大吸收波长为545nm;方法检出限为0.80μg/L;线性范围为4.0~120μg/L,钍(Ⅳ)的标准加入回收率在98.5%~103.6%之间。结合PMBP-甲苯萃取分离,用于测定粉煤灰中的微量钍,结果满意。 相似文献
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Entropy is Key to the Formation of Pentacyclic Terpenoids by Enzyme‐Catalyzed Polycyclization 下载免费PDF全文
Dr. Per‐Olof Syrén Stephan C. Hammer Dr. Birgit Claasen Prof. Dr. Bernhard Hauer 《Angewandte Chemie (International ed. in English)》2014,53(19):4845-4849
Polycyclizations constitute a cornerstone of chemistry and biology. Multicyclic scaffolds are generated by terpene cyclase enzymes in nature through a carbocationic polycyclization cascade of a prefolded polyisoprene backbone, for which electrostatic stabilization of transient carbocationic species is believed to drive catalysis. Computational studies and site‐directed mutagenesis were used to assess the contribution of entropy to the polycyclization cascade catalyzed by the triterpene cyclase from A. acidocaldarius. Our results show that entropy contributes significantly to the rate enhancement through the release of water molecules through specific channels. A single rational point mutation that results in the disruption of one of these water channels decreased the entropic contribution to catalysis by 60 kcal mol?1. This work demonstrates that entropy is the key to enzyme‐catalyzed polycyclizations, which are highly relevant in biology since 90 % of all natural products contain a cyclic subunit. 相似文献