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1.
The NMR spectra of a series of five 3-pyridinols in dioxane and dimethyl sulfoxide have been correlated with electron densities calculated by the Extended Hückel MO method. The data were found to fit a straight line of the form y=ax+b. The effects of hydrogen-bonding between pyridinol molecules on the correlation have been considered, and they have been estimated quantitatively for 6-methyl-3-pyridinol via Extended Hückel Calculations on a hydrogen-bonded model.
Zusammenfassung Die Kernresonanzspektren von fünf 3-Pyridinolen in Dioxan und Dimethylsulfoxyd wurden mit den Elektronendichten aus dem erweiterten Hückelverfahren korreliert, und zwar ergibt sich eine lineare Beziehung. Der Einfluß von intermolekularen Wasserstoffbrücken ist für einen Fall (die 6-Methyl-Verbindung) durch EHT-Rechnungen festgestellt und in den übrigen Fällen geschätzt worden.
Résumé Les spectres NMR d'une série de cinq 3-pyridinols dans le dioxane et le diméthyle-sulfoxyde ont été corrélés avec les densités électroniques calculées par la méthode de Hückel Etendue. Les données se placent correctement sur une droite y=ax+b. Les effets de la liaison hydrogène entre les molécules de pyridinol ont été envisagés et estimés quantitativement pour le 6-méthyl-3-pyridinol par des calculs EHT sur un modèle à liaison hydrogène.相似文献
2.
Michelle Galgoci Janel E. Davidson Clinton K. Harrington Dennis L. Hasha Christian T. Goralski 《合成通讯》2013,43(17):2477-2483
A simple method for the preparation of the title compounds via the reaction of dimethyl 2-ethenylcyclopropane-1,1-dicarboxylate with 6M ammonia in methanol is described. 相似文献
3.
Juliana S Luz Celso RR Ramos Márcia CT Santos Patricia P Coltri Fernando L Palhano Debora Foguel Nilson IT Zanchin Carla C Oliveira 《BMC biochemistry》2010,11(1):22
Background
The archaeal exosome is formed by a hexameric RNase PH ring and three RNA binding subunits and has been shown to bind and degrade RNA in vitro. Despite extensive studies on the eukaryotic exosome and on the proteins interacting with this complex, little information is yet available on the identification and function of archaeal exosome regulatory factors. 相似文献4.
5.
MF Miller IA Franchi AS Sexton CT Pillinger 《Rapid communications in mass spectrometry : RCM》1999,13(13):1211-1217
The use of infrared laser-assisted fluorination to release oxygen from milligram quantities of silicates or other oxide mineral grains is a well-established technique. However, relatively few studies have reported the optimisation of this procedure for oxygen-17 isotope measurements. We describe here details of an analytical system using infrared (10 μm) laser-assisted fluorination, in conjunction with a dual inlet mass spectrometer of high resolving power ( approximately 250) to provide (17)O and (18)O oxygen isotope measurements from 0.5-2 mg of silicates or other oxide mineral grains. Respective precisions (1) of typically 0.08 and 0.04 per thousand are obtained for the complete analytical procedure. Departures from the mass-dependent oxygen isotope fractionation line are quantified by Delta(17)O; our precision (1) of such measurements on individual samples is shown to be +/-0.024 per thousand. In turn, this permits the offset between parallel, mass-dependent fractionation lines to be characterised to substantially greater precision than has been possible hitherto. Application of this system to investigate the (17)O versus (18)O relationship for numerous terrestrial whole-rock and mineral samples, of diverse geological origins and age, indicates that the complete data set may be described by a single, mass-dependent fractionation line of slope 0.5244+/- 0.00038 (standard error). Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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7.
Wenbin Liu KBS Institute of Mathematics Statistics The University of Kent Canterbury CT NF Engl Wei Gong Ningning Yan LSEC 《计算数学(英文版)》2009,(1):97-114
In this paper, we study numerical methods for an optimal control problem with pointwise state constraints. The traditional approaches often need to deal with the deltasingularity in the dual equation, which causes many difficulties in its theoretical analysis and numerical approximation. In our new approach we reformulate the state-constrained optimal control as a constrained minimization problems only involving the state, whose optimality condition is characterized by a fourth order elliptic variational inequality. Then direct numerical algorithms (nonconforming finite element approximation) are proposed for the inequality, and error estimates of the finite element approximation are derived. Numerical experiments illustrate the effectiveness of the new approach. 相似文献
8.
B. Szczepaniak J. Goralski J. Grams W. Maniukiewicz T. Paryjczak 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2007,81(12):1992-1996
A series of ZrO2-TiO2 mixed oxides with different weight ratios (5, 20, and 30% ZrO2) were prepared by wet impregnation of TiO2-P25 Degussa with certain amounts of ZrO(NO3)2·6H2O (Fluka) dissolved in deionised water. The samples were characterized by the XRD,
,
,
, and BET methods. An increase in ZrO2 content shifted the phase transition temperature (anatase into rutile) toward higher temperatures. X-ray diffraction using
an Anton Paar XRK900 reactor chamber indicated that, in the case of samples containing ZrO2, an additional diffraction peak appeared after cooling down to 25°C. This peak could be attributed to a polymorph of TiO2 such as in the single crystal of anatase or hexagonal form of TiO2 which appears in the presence of ZrO2. Generally, the preparation of dioxide systems can modify the properties of pure compounds or generate new catalytic sites
as a result of strong interaction between ZrO2 and TiO2 oxides. The binary systems exhibit advantages like strong acidity, extended specific surface area, and high thermal stability
in comparison with TiO2.
The article is published in the original. 相似文献
9.
Georg Zocher Joachim Vilstrup Daniel Heine Asis Hallab Emilie Goralski Christian Hertweck Mark Stahl Till F. Sch?berle Thilo Stehle 《Chemical science》2015,6(11):6525-6536
Corallopyronin A is a polyketide derived from the myxobacterium Corallococcus coralloides with potent antibiotic features. The gene cluster responsible for the biosynthesis of corallopyronin A has been described recently, and it was proposed that CorB acts as a ketosynthase to interconnect two polyketide chains in a rare head-to-head condensation reaction. We determined the structure of CorB, the interconnecting polyketide synthase, to high resolution and found that CorB displays a thiolase fold. Site-directed mutagenesis showed that the catalytic triad consisting of a cysteine, a histidine and an asparagine is crucial for catalysis, and that this triad shares similarities with the triad found in HMG-CoA synthases. We synthesized a substrate mimic to derivatize purified CorB and confirmed substrate attachment by ESI-MS. Structural analysis of the complex yielded an electron density-based model for the polyketide chain and showed that the unusually wide, T-shaped active site is able to accommodate two polyketides simultaneously. Our structural analysis provides a platform for understanding the unusual head-to-head polyketide-interconnecting reaction catalyzed by CorB. 相似文献
10.
Spencer A. Kerns Junhyeok Seo Vincent M. Lynch Jason Shearer Sean T. Goralski Eileen R. Sullivan Michael J. Rose 《Chemical science》2021,12(38):12838
We report the synthesis and reactivity of a model of [Fe]-hydrogenase derived from an anthracene-based scaffold that includes the endogenous, organometallic acyl(methylene) donor. In comparison to other non-scaffolded acyl-containing complexes, the complex described herein retains molecularly well-defined chemistry upon addition of multiple equivalents of exogenous base. Clean deprotonation of the acyl(methylene) C–H bond with a phenolate base results in the formation of a dimeric motif that contains a new Fe–C(methine) bond resulting from coordination of the deprotonated methylene unit to an adjacent iron center. This effective second carbanion in the ligand framework was demonstrated to drive heterolytic H2 activation across the Fe(ii) center. However, this process results in reductive elimination and liberation of the ligand to extrude a lower-valent Fe–carbonyl complex. Through a series of isotopic labelling experiments, structural characterization (XRD, XAS), and spectroscopic characterization (IR, NMR, EXAFS), a mechanistic pathway is presented for H2/hydride-induced loss of the organometallic acyl unit (i.e. pyCH2–C O → pyCH3+C O). The known reduced hydride species [HFe(CO)4]− and [HFe3(CO)11]− have been observed as products by 1H/2H NMR and IR spectroscopies, as well as independent syntheses of PNP[HFe(CO)4]. The former species (i.e. [HFe(CO)4]−) is deduced to be the actual hydride transfer agent in the hydride transfer reaction (nominally catalyzed by the title compound) to a biomimetic substrate ([TolIm](BArF) = fluorinated imidazolium as hydride acceptor). This work provides mechanistic insight into the reasons for lack of functional biomimetic behavior (hydride transfer) in acyl(methylene)pyridine based mimics of [Fe]-hydrogenase.We report the synthesis and reactivity of a model of [Fe]-hydrogenase derived from an anthracene-based scaffold that includes the endogenous, organometallic acyl(methylene) donor. 相似文献