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1.
RNA as an RNA polymerase: net elongation of an RNA primer catalyzed by the Tetrahymena ribozyme 总被引：7，自引：0，他引：7
A catalytic RNA (ribozyme) derived from an intervening sequence (IVS) RNA of Tetrahymena thermophila will catalyze an RNA polymerization reaction in which pentacytidylic acid (C5) is extended by the successive addition of mononucleotides derived from a guanylyl-(3',5')-nucleotide (GpN). Cytidines or uridines are added to C5 to generate chain lengths of 10 to 11 nucleotides, with longer products being generated at greatly reduced efficiency. The reaction is analogous to that catalyzed by a replicase with C5 acting as the primer, GpNs as the nucleoside triphosphates, and a sequence in the ribozyme providing a template. The demonstration that an RNA enzyme can catalyze net elongation of an RNA primer supports theories of prebiotic RNA self-replication. 相似文献
2.
The rhodium porphyrin-catalyzed cyclopropanation of alkenes by ethyl diazoacetate (EDA) is representative of a number of metal-mediated cyclopropanation reactions used widely in organic synthesis. The active intermediate in these reactions is thought to be a metal carbene complex, but evidence for the involvement of metal-olefin pi complexes has also been presented. Low-temperature infrared and nuclear magnetic resonance spectroscopies have been used to characterize a rhodium porphyrin-diazoalkyl adduct that results from the stoichiometric condensation of the catalyst and EDA. Optical spectroscopy suggests that this complex is the dominant steady-state species in the catalytic reaction. This compound decomposes thermally to provide cyclopropanes in the presence of styrene, suggesting that the carbene is indeed the active intermediate. Metal-alkene pi complexes have also been detected spectroscopically. Kinetic studies suggest that they mediate the rate of carbene formation from the diazoalkyl complex but are not attacked directly by EDA. 相似文献
3.
H Nam NE Lewis JA Lerman DH Lee RL Chang D Kim BO Palsson 《Science (New York, N.Y.)》2012,337(6098):1101-1104
Enzymes are thought to have evolved highly specific catalytic activities from promiscuous ancestral proteins. By analyzing a genome-scale model of Escherichia coli metabolism, we found that 37% of its enzymes act on a variety of substrates and catalyze 65% of the known metabolic reactions. However, it is not apparent why these generalist enzymes remain. Here, we show that there are marked differences between generalist enzymes and specialist enzymes, known to catalyze a single chemical reaction on one particular substrate in vivo. Specialist enzymes (i) are frequently essential, (ii) maintain higher metabolic flux, and (iii) require more regulation of enzyme activity to control metabolic flux in dynamic environments than do generalist enzymes. Furthermore, these properties are conserved in Archaea and Eukarya. Thus, the metabolic network context and environmental conditions influence enzyme evolution toward high specificity. 相似文献
4.
Transport studies in bacterial membrane vesicles 总被引：43，自引：0，他引：43
H R Kaback 《Science (New York, N.Y.)》1974,186(4167):882-892
The use of bacterial membrane vesicles as an experimental system for the study of active transport has been discussed. Vesicles are prepared from osmotically sensitized bacteria, and consist of osmotically intact, membranebound sacs without internal structure. They retain litle or no cytoplasm. Under appropriate conditions, these vesicles catalyze the transport of a variety of solutes at rates which are comparable, in many cases, to those of intact cells. Two general types of transport systems have been elucidated in the vesicle system: (i) group translocation systems which catalyze vectorial covalent reactions; and (ii) respirationlinked transport systems that catalyze the active transport of a whole range of metabolites against an electrochemical or osmotic gradient. In E. coli membrane vesicles, the respiration-linked transport systems are coupled primarily to the oxidation of (D)-lactate to pyruvate, catalyzed by a flavin-linked, membrane-bound (D)-lactate dehydrogenase which has been purified to homogeneity. Electrons derived from (D)-lactate or certain artificial electron donors are transferred to oxygen by means of a membrane-bound respiratory chain, and respiration is coupled to active transport within a segment of the respiratory chain between the primary dehydrogenase and cytochrome. b(l). The great majority of the individual membrane vesicles in the population catalyze active transport, and the generation or hydtolysis of ATP is not involved. Under anaerobic conditions, fumarate or nitrate can be utilized in place of oxygen as terminal electron acceptors. With the exception that (D)-lactate is not always the most effective electron donor for active transport, vesicles prepared from a number of other organisms catalyze transport in a similar manner. Fluorescent dansylgalactosides are useful molecular probes of active transport in the vesicle system. These compounds are competitive inhibitors of beta-galactoside transport, but are not transported themselves. Fluorescence studies indicate that the lac carrier protein constitutes approximately 3 to 6 percent of the total membrane protein, and that it is not accessible to the external medium unless the membrane is "energized." Thus, energy is coupled to one of the initial steps in the transport process. Studies with a photoaffinity-labeled galactoside provide independent support for this conclusion. When membrane vesicles prepared from a (D)-lactate dehydrogenase mutant of E. coli are treated with (D)-lactate dehydrogenase, the enzyme binds to the vesicles and they regain the capacity to catalyze (D)-lactate oxidation and (D)-lactate-dependent active transport. The maximal specific transport activity obtained in the reconstituted system is similar in magnitude to that of wildtype vesicles. Titration studies with dansylgalactoside demonstrate that there is at least a seven- to eightfold excess of lac carrier protein relative to (D)-lactate dehydrogenase. Evidence is presented indicating that the enzyme is bound to the inner surface of native membrane vesicles and to the outer surface of reconstituted vesicles, and that the flavin coenzyme moiety is critically involved in binding. Possible mechanisms of respirationlinked active transport are discussed. 相似文献
5.
The industrially important coupling of aromatic compounds has generally required differential prefunctionalization of the arene coupling partners with a halide and an electropositive group. Here we report that palladium, in conjunction with a copper oxidant, can catalyze the cross-coupling of N-acetylindoles and benzenes in high yield and high regioselectivity across a range of indoles without recourse to activating groups. These reactions are completely selective for arene cross-coupling, with no products arising from indole or benzene homo-coupling detected by spectroscopic analysis. This efficient reactivity should be useful in the design of other oxidative arene cross-couplings as well. 相似文献
6.
7.
Transition metal complexes catalyze many important reactions that are employed in medicine, materials science, and energy production. Although high-throughput methods for the discovery of catalysts that would mirror related approaches for the discovery of medicinally active compounds have been the focus of much attention, these methods have not been sufficiently general or accessible to typical synthetic laboratories to be adopted widely. We report a method to evaluate a broad range of catalysts for potential coupling reactions with the use of simple laboratory equipment. Specifically, we screen an array of catalysts and ligands with a diverse mixture of substrates and then use mass spectrometry to identify reaction products that, by design, exceed the mass of any single substrate. With this method, we discovered a copper-catalyzed alkyne hydroamination and two nickel-catalyzed hydroarylation reactions, each of which displays excellent functional-group tolerance. 相似文献
8.
9.
Zhang C Griffith BR Fu Q Albermann C Fu X Lee IK Li L Thorson JS 《Science (New York, N.Y.)》2006,313(5791):1291-1294
Glycosyltransferases (GTs), an essential class of ubiquitous enzymes, are generally perceived as unidirectional catalysts. In contrast, we report that four glycosyltransferases from two distinct natural product biosynthetic pathways-calicheamicin and vancomycin-readily catalyze reversible reactions, allowing sugars and aglycons to be exchanged with ease. As proof of the broader applicability of these new reactions, more than 70 differentially glycosylated calicheamicin and vancomycin variants are reported. This study suggests the reversibility of GT-catalyzed reactions may be general and useful for generating exotic nucleotide sugars, establishing in vitro GT activity in complex systems, and enhancing natural product diversity. 相似文献
10.
Expression of bovine 17 alpha-hydroxylase cytochrome P-450 cDNA in nonsteroidogenic (COS 1) cells 总被引：12，自引：0，他引：12
Cortisol production requires the activity of only 17 alpha-hydroxylase, whereas the formation of sex steroids requires both 17 alpha-hydroxylase and 17,20-lyase activities. Studies in reconstituted enzyme systems have suggested that a single steroid hydroxylase, 17 alpha-hydroxylase cytochrome P-450 (P-450(17) alpha), catalyzes both activities. By expression of bovine adrenocortical P-450(17 alpha) in COS 1 (transformed monkey kidney) cells, which normally contain no detectable P-450(17) alpha, it has now been established in situ that a single polypeptide chain does catalyze both the 17 alpha-hydroxylase and the 17,20-lyase reactions. This heterologous system supports 17 alpha-hydroxylation of pregnenolone and progesterone with equal efficiency, but catalyzes about five times as much 17,20-lyase activity when 17 alpha-hydroxypregnenolone is the substrate than when 17 alpha-hydroxyprogesterone is the substrate. For these activities to be observed in COS 1 cells, newly synthesized apocytochrome P-450(17) alpha must bind heme and insert into the endoplasmic reticulum such that endogenous cytochrome P-450 reductase can support hydroxylation. Thus, COS 1 cells are a useful system for expression and study of various forms of cytochrome P-450. 相似文献
11.
试验将青蒿素生物合成途径中催化两步连续反应的酶(法呢基焦磷酸合酶和紫穗槐二烯合酶)的基因进行融合,经大肠杆菌表达后鉴定其融合蛋白的功能。结果表明:融合蛋白具有了双功能酶活性。双功能酶基因的构建,为进一步将双功能酶基因转入黄花蒿,提高青蒿素含量奠定了基础。 相似文献
12.
油松树冠枝生长规律的探讨 总被引：5，自引：0，他引：5
韩兴吉 《北京林业大学学报》1985,(3)
本文利用生长比的概念探讨了油松枝的延长生长量随着枝龄和着枝深度而变化的规律。并利用枝解析方法研究了枝的材积生长与枝龄、着枝深度和树木所处的竞争状态间的关系,最后确定出各样木总枝材积的生长及枝、干材积生长的比例。研究结果表明:树冠内枝的年延长生长在树冠顶端第二轮或第三轮枝处达到最大值;而枝材积生长的最大值则在较下部的轮枝上出现,具体位置与树冠的大小和所承受的竞争压力有关;不同样木的枝、干材积生长比例相差很大,孤立木可达1:1,而被压木却只有1:10左右,从中说明树木间的竞争对枝材积生长的影响比对干材积生长的影响更大。 相似文献
13.
Defining the inside and outside of a catalytic RNA molecule 总被引：42，自引：0，他引：42
Ribozymes are RNA molecules that catalyze biochemical reactions. Fe(II)-EDTA, a solvent-based reagent which cleaves both double- and single-stranded RNA, was used to investigate the structure of the Tetrahymena ribozyme. Regions of cleavage alternate with regions of substantial protection along the entire RNA molecule. In particular, most of the catalytic core shows greatly reduced cleavage. These data constitute experimental evidence that an RNA enzyme, like a protein enzyme, has an interior and an exterior. Determination of positions where the phosphodiester backbone of the RNA is on the inside or on the outside of the molecule provides major constraints for modeling the three-dimensional structure of the Tetrahymena ribozyme. This approach should be generally informative for structured RNA molecules. 相似文献
14.
Laszlo P 《Science (New York, N.Y.)》1987,235(4795):1473-1477
Layer aluminosilicates catalyze reactions in numerous ways. They stabilize high-energy intermediates. They can store energy in their lattice structures and can release it in the form of chemical energy. They can catalyze redox reactions and can serve as photocatalytic devices. They often exhibit high surface acidity. Organic reactions that are catalyzed by the agency of days are reviewed. The role of clays in prebiotic chemistry is also examined. 相似文献
15.
泡桐下侧芽萌发成枝与上侧芽萌发接干间关系 总被引：14，自引：0，他引：14
该文研究了自然状态下1年生泡桐下侧芽萌发成枝与上侧芽萌发接干间的关系.结果显示:在高密度林分的接干单株中,上侧芽萌发成枝接干与下侧芽萌发成枝间关系密切.接干侧芽的对生侧芽萌发不利于接干枝高生长,并降低接干形率;接干处向下数第1对侧芽萌发成枝倾角越小接干形率越高,第1、2对侧枝长度和粗度仅与胸径生长正相关;第3对侧枝倾角与接干处主干直径和接干基径呈负相关.增加成枝数量,减少单枝生长量,而枝长、基径合计不减少,能增大接干高度和接干处主干直径;第4对侧枝长度、粗度与主干、接干粗生长正相关;第5对侧枝长度、粗度与胸径生长正相关,而其以下侧枝对主干和接干的生长影响较小. 相似文献
16.
植物的分枝过程对研究植物的生长规律有重要的意义。借助于马尔科夫链模型,定量化研究了紫花苜蓿枝条的分枝过程。依据苜蓿枝条的分枝特点,以组成枝条的节间作为马尔科夫链的状态;状态的划分以节(或者节间)上发生的下级枝条加以区别,并进一步计算得到马尔科夫链模型的初始化矩阵、一阶转移概率矩阵与二阶转移概率矩阵。在此基础上,采用马尔科夫模型模拟预测了苜蓿枝条的分枝变化过程。通过田间两个品种苜蓿栽培观测试验,获取马尔科夫链模型的参数,并进行了苜蓿枝条分枝过程的模拟。模拟结果显示,马尔科夫链模型模拟的枝条分枝结果与实际的统计结果比较吻合。表明马尔科夫链模型能够用来描述苜蓿枝条的分枝过程。 相似文献
17.
Fatty alcohols (normal and isoprenoid) in sediments 总被引：1，自引：0，他引：1
Normal long-chain alcohols were isolated from Recent marine sediments from several environments. The isoprenoid alcohol dihydrophytol, which is thought to originate from phytol, the side chain of chlorophyll, by hydrogenation in the reducing environment of the sediment, was also present in most of the samples. Both the normal and isoprenoid alcohols were found in the Green River shale (Eocene). Geochemical implications are considered. 相似文献
18.
Many cellular reactions involve both hydrophobic and hydrophilic molecules that reside within the chemically distinct environments defined by the phospholipid-based membranes and the aqueous lumens of cytoplasm and organelles. Enzymes performing this type of reaction are required to access a lipophilic substrate located in the membranes and to catalyze its reaction with a polar, water-soluble compound. Here, we explore the different binding strategies and chemical tricks that enzymes have developed to overcome this problem. These reactions can be catalyzed by integral membrane proteins that channel a hydrophilic molecule into their active site, as well as by water-soluble enzymes that are able to capture a lipophilic substrate from the phospholipid bilayer. Many chemical and biological aspects of this type of enzymology remain to be investigated and will require the integration of protein chemistry with membrane biology. 相似文献
19.
The chemistry of self-splicing RNA and RNA enzymes 总被引：59，自引：0，他引：59
T R Cech 《Science (New York, N.Y.)》1987,236(4808):1532-1539
Proteins are not the only catalysts of cellular reactions; there is a growing list of RNA molecules that catalyze RNA cleavage and joining reactions. The chemical mechanisms of RNA-catalyzed reactions are discussed with emphasis on the self-splicing ribosomal RNA precursor of Tetrahymena and the enzymatic activities of its intervening sequence RNA. Wherever appropriate, catalysis by RNA is compared to catalysis by protein enzymes. 相似文献
20.
玉米淀粉分支酶基因启动子的克隆及生物信息学分析 总被引：1，自引：0，他引：1
[目的]为了研究不同淀粉含量的启动子之间是否有差异及对直链淀粉合成途径是否有影响.[方法]以常规玉米叶片基因组DNA为模板,利用NCBI网站公布的高直链玉米淀粉分支酶基因(Zea mays starch branching enzyme IIb,SBEIIb)序列设计引物,通过PCR反应扩增出常规玉米淀粉分支酶基因的启动子序列,将该扩增片段与T载体连接后测序,并与高直链玉米淀粉分支酶基因启动子的序列进行比较分析.[结果]结果表明:玉米淀粉分支酶基因启动子与公布的启动子序列同源性高达99.3%,序列差异Pi值为0.007 16,该差异主要是SNP(单核苷酸多态性)和Indel(插入/缺失)造成的,推测该差异可能会影响到淀粉分支酶基因的表达,是造成玉米直链淀粉含量差异的因素之一.[结论]该研究为深入了解玉米直链淀粉合成机理提供了重要依据. 相似文献