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51.
We present MNDO calculations of a series of nine-membered conjugated compounds. The geometries have been fully optimized. Cyclononatetraenyl and benzocyclononatetraenyl anions, nonapyrrol, and nonathiophene appear to be planar aromatic compounds. Following MNDO , nonafulvene has a planar prefered conformation, but a polyenic structure, while nonafuran and cyclononatetraene are gauche molecules. The Universal Huckel Method (UHM ), a simple all valence electron empirical technique which describes σ systems using localized MO , gives, qualitatively, the same results as the MNDO method. The quantum calculation carried out with MNDO and UHM have been used to describe the physicochemical properties of ninememberedring conjugated compounds under consideration. To our knowledge, we present here the first theoretical study dealing with nine-membered conjugated molecules. 相似文献
52.
Functionalized keto-enamines 6 were obtained by nucleophilic addition of enol ethers to the imine moiety of 2-azadienes derived from dehydroaspartic esters 4. Reactions of 2-azadiene 4c containing three electron-withdrawing substituents (CO(2)R) with enol ethers 5 in the presence of lithium perchlorate led to the formation of tetrahydropyridine derivatives 7 in a regio- and stereoselective fashion. 2H-[1,3]-oxazines 10 and pyridine derivatives 12 and 13 were obtained by heterocycloaddition reactions of electron-poor azadienes 4d-g containing two electron-withdrawing substituents (4-O(2)N-C(6)H(4), CO(2)R) in positions 1 and 4 with carbonyl derivatives (ethyl glyoxalate 9a and diethyl ketomalonate 9b) and the electron-deficient olefin tetracyanoethylene 11. 相似文献
53.
Lainez A del Burgo P Junquera E Aicart E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5745-5752
Speed of sound, density, conductivity, and fluorescence spectroscopy experiments were run to analyze the mixed aggregation process of a nonionic-cationic surfactant system in aqueous media at 298.15 K. The mixed system comprises a nonionic surfactant, n-octyl-beta-D-glucopyranoside (OBG), and a cationic surfactant, tetradecyltrimethylammonium bromide (C14TAB), with 8 and 14 carbon atoms on the hydrophobic tails, respectively. From these data, the total and partial critical micellar concentrations, the total and partial aggregation numbers, apparent molar volumes and isentropic compressibilities, hydration numbers, and the corresponding changes in the latest properties due to the mixed aggregation process were determined. Pure and mixed micelles were analyzed from a geometrical point of view by determining the packing parameter of the aggregates. Furthermore, the experimental characterization of both the monomeric and micellar phases was completed with a theoretical study of the mixed micellization phenomena studied herein, by means of some of the most relevant theoretical models. 相似文献
54.
Keith B. Oldham Terence J. Cardwell Jose H. Santos Alan M. Bond 《Journal of Electroanalytical Chemistry》1997,430(1-2)
Voltammetric studies in solutions of high resistivity are facilitated by the use of microelectrodes under steady-state conditions. Such solutions are encountered with solvents of low permittivity because of the very sparing solubility of electrolytes. Moreover, in such media the supporting electrolyte, as well as the electroactive ionic species, is usually extensively ion paired. Here we predict the limiting current that will flow in these circumstances, when a monovalent ion undergoes a one-electron transfer at a hemispherical microelectrode to form a neutral product. The ion pairing equilibria are assumed to be fast but all diffusion coefficients are treated as distinct. An analytical solution is elusive in the general case, but a simple numerical procedure allows the limiting current to be predicted for any combination of the system parameters. Several special cases are also discussed, some of which yield explicit formulae for the limiting current. In a companion paper, experimental data are compared with the theoretical predictions. 相似文献
55.
Numerical solution of delay differential equations by uniform corrections to an implicit Runge-Kutta method 总被引:3,自引:0,他引:3
Summary In this paper we develop a class of numerical methods to approximate the solutions of delay differential equations. They are essentially based on a modified version, in a predictor-corrector mode, of the one-step collocation method atn Gaussian points. These methods, applied to ODE's, provide a continuous approximate solution which is accurate of order 2n at the nodes and of ordern+1 uniformly in the whole interval. In order to extend the methods to delay differential equations, the uniform accuracy is raised to the order 2n by some a posteriori corrections. Numerical tests and comparisons with other methods are made on real-life problems.This work was supported by CNR within the Progetto Finalizzato Informatica-Sottopr. P1-SOFMAT 相似文献
56.
Qi ZM Matsuda N Santos J Yoshida T Takatsu A Kato K 《Journal of colloid and interface science》2004,271(1):249-253
Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode. 相似文献
57.
58.
The dynamic behaviour of [Pt(/gh3-allyl){P(cyclohexyl)3}2]+[PF6]- has been reinvestigated, and the earlier interpretation of restricted rotation about the Pt—P endorsed. The activation parameters were obtained. [Pt(/gh3-allyl)(PPri3)2]+[PF6]- behaves similarly, while it has not prove possible to stop the rotation in [Pt(/gh3-allyl){P(CH2Ph)3}2]+[PF6]-. 相似文献
59.
Zhu L Ostash B Rix U Nur-E-Alam M Mayers A Luzhetskyy A Mendez C Salas JA Bechthold A Fedorenko V Rohr J 《The Journal of organic chemistry》2005,70(2):631-638
The angucycline antibiotic family of the landomycins displays potent antitumor activity. To elucidate early post polyketide synthase (PKS) tailoring steps of the landomycin E biosynthetic pathway in Streptomyces globisporus 1912, the mutant S. globisporus M12 was prepared through gene replacement experiment of lndM2. It encodes an enzyme with putative oxygenase and reductase domains, according to sequencing of the gene and its counterpart lanM2 from S. cyanogenus S136 landomycin A biosynthetic gene cluster. The isolation of the novel shunt products 11-hydroxytetrangomycin and 4-hydroxytetrangomycin along with the well-known angucyclines tetrangomycin and tetrangulol from the culture of S. globisporus M12 provides evidence for the involvement of lndM2 in the early biosynthetic pathway of the landomycins, in particular in the formation of the alicyclic 6-hydroxy function of the landomycin aglycon. We therefore propose LndM2 to be responsible for both hydroxylation of the 6-position and its subsequent reduction. These reactions are necessary before the glycosylation reactions can occur. The results are in agreement with the originally published structure of landomycin but do not support the recently suggested revised structure. 相似文献
60.
Arsenic Speciation in Urine and Blood Reference Materials 总被引:1,自引:0,他引:1
Todor I. Todorov John W. Ejnik Florabel G. Mullick Jose A. Centeno 《Mikrochimica acta》2005,151(3-4):263-268
Acute and chronic exposure to arsenic is a growing problem in the industrialized world. Arsenic is a potent carcinogen and
toxin in humans. In the body, arsenic is metabolized to produce several species, including inorganic forms, such as trivalent
(AsIII) and pentavalent (AsV), and the methylated metabolites such as monomethylarsonic acid, (MMAV), and dimethylarsinic acid (DMAV), in addition to arsenobetaine (AsB) which is ingested and excreted from the body in the same form. Each of these species
has been reported to possess a specific but different degree of toxicity. Thus, not only is the measurement of total As required,
but also quantification of the individual metabolites is necessary to evaluate the toxicity and risk assessment of this element.
There are a large number of reference materials that are used to validate methodology for the analysis of As in blood and
urine, but they are limited to total As concentrations. In this study, the speciation of five arsenic metabolites is reported
in blood and urine from commercial available control materials certified for total arsenic levels. The separation was performed
with an anion exchange column using inductively coupled plasma mass spectrometry as a detector. Baseline separation was achieved
for AsIII, AsV, MMAV, DMAV, and AsB, allowing us to quantify all five species. Excellent agreement between the total arsenic levels and the sum of the
speciated As levels was obtained. 相似文献