共查询到20条相似文献，搜索用时 31 毫秒
1.
采用微波协助加热的联氨还原工艺快速合成了纳米Ni粉,并利用X-射线粉末衍射仪(XRD)、透射电子显微镜(TEM)、比表面仪(BET)等测试方法对其结构、形貌和比表面积进行了表征,并用差热分析法(DTA)研究了纳米Ni粉对高氯酸铵(AP)热分解的催化效果。结果表明,微波合成工艺法不仅速度快、反应条件简单、重现性好,而且所得的纳米Ni粉结晶好、分散性好,比表面积大。当其质量分数5%时,可使AP的高温分解峰温度降低了99.25°C,表观分解热增加了960 J/g,表现出对AP热分解具有显著的催化性能,明显优于传统水浴加热法所制得的纳米Ni粉催化剂。 相似文献
2.
[目的]研究酸酐修饰对脂肪酶催化性能的作用。[方法]采用琥珀酸酐、丙酸酐和乙酸酐对Novozym 435脂肪酶进行了修饰,优化修饰条件,并对修饰后Novozym 435的催化性能进行测定。[结果]酸酐修饰可显著提高Novozym 435脂肪酶的水解活性。琥珀酸酐修饰Novozym 435酶活为79.3 U/g,相对于未修饰酶酶活（63.9 U/g）,提高了24%;丙酸酐修饰后酶活为85.6 U/g,提高了33.9%;而乙酸酐修饰后酶活为84.0 U/g,提高了31.4%。而且酸酐修饰后酶的热稳定性、pH稳定性和耐有机溶剂的能力也都有很大提高。[结论]酸酐修饰是一种有效的提高脂肪酶催化性能的重要方法。 相似文献
3.
The formation of a single product from terminal functionalization of linear alkanes from a transition metal-catalyzed reaction is reported. The rhodium complex Cp*Rh(eta(4)-C(6)Me(6)) (Cp*, C(5)Me(5); Me, methyl) catalyzes the high-yield formation of linear alkylboranes from commercially available borane reagents under thermal conditions. These reactions now allow catalytic, regiospecific functionalization of alkanes under thermal conditions. The organoborane products are among the most versatile synthetic intermediates in chemistry and serve as convenient precursors to alcohols, amines, and other common classes of functionalized molecules. 相似文献
4.
A series of free-radical catalysts have been discovered that increase the yield of highly valuable olefins from the cracking of low molecular weight paraffins. For example, catalytic cracking of n-butane, isobutane, and propane over manganese or iron supported on magnesium oxide (MgO) gave product distributions different from those given by thermal (free-radical) cracking or cracking over traditional acid catalysts. With n-butane and propane feeds, the products from catalytic cracking included large amounts of ethylene and ethane; with isobutane feed, propylene was the major product. Physical characterization of the MgO-supported catalyst showed the manganese to be in a 2+ oxidation state in the reduced catalyst and a 4+ oxidation state in the fully oxidized catalyst. Manganese was also shown to be uniformly distributed in the support material with very little enrichment at the surface. Matrix isolation of the gasphase radicals from n-butane feed showed that ethyl and methyl radicals were produced over the active catalysts. In the thermal process, only methyl radicals were produced. The mechanism of the catalytic reaction appears to be selective formation of primary carbanions at the catalyst surface followed by electron transfer and release of primary hydrocarbon radicals to the gas phase. 相似文献
5.
W Wang G McCool N Kapur G Yuan B Shan M Nguyen UM Graham BH Davis G Jacobs K Cho X Hao 《Science (New York, N.Y.)》2012,337(6096):832-835
Oxidation of nitric oxide (NO) for subsequent efficient reduction in selective catalytic reduction or lean NO(x) trap devices continues to be a challenge in diesel engines because of the low efficiency and high cost of the currently used platinum (Pt)-based catalysts. We show that mixed-phase oxide materials based on Mn-mullite (Sm, Gd)Mn(2)O(5) are an efficient substitute for the current commercial Pt-based catalysts. Under laboratory-simulated diesel exhaust conditions, this mixed-phase oxide material was superior to Pt in terms of cost, thermal durability, and catalytic activity for NO oxidation. This oxide material is active at temperatures as low as 120°C with conversion maxima of ~45% higher than that achieved with Pt. Density functional theory and diffuse reflectance infrared Fourier transform spectroscopy provide insights into the NO-to-NO(2) reaction mechanism on catalytically active Mn-Mn sites via the intermediate nitrate species. 相似文献
6.
Zweig G 《Science (New York, N.Y.)》1978,201(4360):973-979
7.
Mango FD 《Science (New York, N.Y.)》1987,237(4814):514-517
Four isoheptanes in petroleum display a remarkable invariance in a ratio of sums of concentrations. The isoheptanes are not at thermodynamic equilibrium, nor are they fixed to some constant composition. The four isomers display coherent change in relative amounts but maintain invariance in the ratio of sums. Within sets of genetically related petroleum samples, invariance reaches levels that approach the limits of our analytical precision. The invariance is inconsistent with a chemical origin that involves the thermal fragmentation of natural products or their derivatives. It suggests a reaction process at steady state, in which relative rates of product formation are constant. A mechanism is proposed in which the four isoheptanes are formed pairwise and sequentially through two intermediates in a catalytic process that operates at steady state. 相似文献
8.
The response of living cells to very weak electric fields: the thermal noise limit 总被引：16，自引：0，他引：16
A physical model in which cells are considered as possible detectors of very weak periodic electric fields yields a general relation between cell size and both thermally induced fluctuations in membrane potential and the maximum change in membrane potential caused by an applied field. The simplest version of the model provides a broad-band estimate of the smallest applied electric field to which membrane macromolecules can directly respond (about 10(-3) volt per centimeter). Much smaller fields (10(-6) volt per centimeter) can be detected if there is a response in only a narrow band of frequencies or if signal averaging occurs through field-induced variation in the catalytic activity of membrane-associated enzymes. Both extensions of the simplest version remove the apparent violation of the thermal noise limit found in some experiments. 相似文献
9.
[目的]高温热处理可使木材半纤维素部分降解,改善木材的尺寸稳定性.使用外源酸可降低木材半纤维素热降解温度,因此有必要明确其热降解规律.[方法]采用碱法分离的方式提取出杨木和杉木的半纤维素,通过傅里叶红外光谱仪和热重分析法研究引入外源酸条件下(两种外源酸AlCl3和H3PO4,每种外源酸的浓度分别为0.1和0.3 mol... 相似文献
10.
稠油集输中催化裂化降粘技术的研究 总被引：7，自引：2，他引：5
分析了稠油粘度高、胶质沥青质含量高的根本原因,针对常规输油工艺的特点及存在的问题,提出了矿场催化裂化降粘的新思路,催化裂化主要是将稠油含碳数多的稠油大分子降解为含碳数少的轻质油小分子。阐述了稠油催化裂化及降粘原理,指出低温高效的稠油裂化催化剂的筛选、热驱方式的选择及矿场稠油裂化装置的布置与规划是该种新技术的关键。 相似文献
11.
Engineering enzyme specificity by "substrate-assisted catalysis" 总被引：8，自引：0，他引：8
A novel approach to engineering enzyme specificity is presented in which a catalytic group from an enzyme is first removed by site-directed mutagenesis causing inactivation. Activity is then partially restored by substrates containing the missing catalytic functional group. Replacement of the catalytic His with Ala in the Bacillus amyloliquefaciens subtilisin gene (the mutant is designated His64Ala) by site-directed mutagenesis reduces the catalytic efficiency (kcat/Km) by a factor of a million when assayed with N-succinyl-L-Phe-L-Ala-L-Ala-L-Phe-p-nitroanilide (sFAAF-pNA). Model building studies showed that a His side chain at the P2 position of a substrate bound at the active site of subtilisin could be virtually superimposed on the catalytic His side chain of this serine protease. Accordingly, the His64Ala mutant hydrolyzes a His P2 substrate (sFAHF-pNA) up to 400 times faster than a homologous Ala P2 or Gln P2 substrate (sFAAF-pNA or sFAQF-pNA) at pH 8.0. In contrast, the wild-type enzyme hydrolyzes these three substrates with similar catalytic efficiencies. Additional data from substrate-dependent pH profiles and hydrolysis of large polypeptides indicate that the His64Ala mutant enzyme can recover partially the function of the lost catalytic histidine from a His P2 side chain on the substrate. Such "substrate-assisted catalysis" provides a new basis for engineering enzymes with very narrow and potentially useful substrate specificities. These studies also suggest a possible functional intermediate in the evolution of the catalytic triad of serine proteases. 相似文献
12.
13.
Tews I Findeisen F Sinning I Schultz A Schultz JE Linder JU 《Science (New York, N.Y.)》2005,308(5724):1020-1023
Class III adenylyl cyclases contain catalytic and regulatory domains, yet structural insight into their interactions is missing. We show that the mycobacterial adenylyl cyclase Rv1264 is rendered a pH sensor by its N-terminal domain. In the structure of the inhibited state, catalytic and regulatory domains share a large interface involving catalytic residues. In the structure of the active state, the two catalytic domains rotate by 55 degrees to form two catalytic sites at their interface. Two alpha helices serve as molecular switches. Mutagenesis is consistent with a regulatory role of the structural transition, and we suggest that the transition is regulated by pH. 相似文献
14.
催化动力学电位法测定海产品中微量碘 总被引：1，自引：0，他引：1
[目的]建立一种测定海产品中微量碘的催化动力学电位法。[方法]采用单因素试验考察了催化动力学电位法测定海产品中微量碘的影响因素,并测定了海带（Laminaria japonica）、紫菜（Porphyra teneraKjellman）和海虾中碘的含量。[结果]建立的催化动力学电位法测定碘含量的线性范围为8-28 ng/ml,方法的检出限为5.2 ng/ml,回收率大于97.0%,相对标准偏差（RSD）小于1.1%,方法准确可靠。采用该法测定的海带、紫菜和海虾中碘的含量分别为31.98、27.38、18.40μg/g,RSD分别为1.48%、0.70%、1.61%。[结论]该研究建立的方法不需要避光,操作简单,温度控制方便,用于海产品中微量碘的测定结果令人满意。 相似文献
15.
应用断裂力学理论和实验技术,测定了重油催化再生器材料及焊缝的力学性能和断裂韧度值,按照《压力容器缺陷评定规范》(CVDA-84)对再生器下部筒体典型缺陷进行了评定。经分析计算获得了重油催化再生器下部筒体各部位各种裂纹类型缺陷的允许尺寸,可将其作为重油催化再生器无损检测时的缺陷评定指标。 相似文献
16.
Homogeneous catalytic activation of the strong carbon-fluorine bonds under mild conditions was achieved with the use of rhodium complexes as catalysts. The catalytic reactions between polyfluorobenzenes and hydrosilanes result in substitution of fluorine atoms by hydrogen atoms and are chemo- and regioselective. With individual stoichiometric steps observed and combined, and with intermediates isolated and fully characterized (including crystal structures), these systems demonstrate the effectiveness of a rational approach to catalytic design. 相似文献
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18.
通过对毛白杨中的4--香豆酸:辅酶A连接酶1（Pt4CL1）蛋白第338位缬氨酸进行缺失突变,从而获得了具有芥子酸催化活性的Pt4CL1蛋白突变体338dVal。与野生型4CL1蛋白活性相比较,该突变体获得了催化芥子酸的活性,比活力是(162±034) nkat/mg。同时,对4--香豆酸催化活性有轻微的降低（约降低12％）,对咖啡酸的催化活性有明显增加（约增加126％）,对阿魏酸的催化活性有部分的降低（约降低29％）,对肉桂酸的催化活性没有显著变化。该结论证实了第338位缬氨酸对底物芥子酸5位甲氧基具有空间位阻效应。该项研究为通过基因工程技术调控木质素的合成提供了新的方法。 相似文献
19.
A mutation in the catalytic subunit of cAMP-dependent protein kinase that disrupts regulation 总被引：8，自引：0，他引：8
L R Levin J Kuret K E Johnson S Powers S Cameron T Michaeli M Wigler M J Zoller 《Science (New York, N.Y.)》1988,240(4848):68-70
A mutant catalytic subunit of adenosine 3',5'-monophosphate (cAMP)-dependent protein kinase has been isolated from Saccharomyces cerevisiae that is no longer subject to regulation yet retains its catalytic activity. Biochemical analysis of the mutant subunit indicates a 100-fold decreased affinity for the regulatory subunit. The mutant catalytic subunit exhibits approximately a threefold increase in Michaelis constant for adenosine triphosphate and peptide cosubstrates, and is essentially unchanged in its catalytic rate. The nucleotide sequence of the mutant gene contains a single nucleotide change resulting in a threonine-to-alanine substitution at amino acid 241. This residue is conserved in other serine-threonine protein kinases. These results identify this threonine as an important contact between catalytic and regulatory subunits but only a minor contact in substrate recognition. 相似文献
20.
采用Pt-Rh催化器净化方法,并着重探讨了以降低NO排放为主的Pt-Rh催化器性能、排放温度、NO还原催化的性能和转化效率控制等问题。试验研究了Pt-Rh催化器的转化效果、其间的相互影响和作用,并提出相应的排放建议。结果表明:当贵金属Rh的加入量为30g时,Pt-Rh催化器可有效降低小型汽油机的NO排放量,最高转化效率达到48%,同时对HC、CO的排放也有一定的降解作用。 相似文献