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1.
Résumé Une étude théorique ab initio SCF-LCAO-MO de la méthylène imine et de l'anion vinyle a été effectuée. Les barrières d'énergie calculées pour l'inversion de l'azote et pour la rotation autour de la liaison C=N sont respectivement de 26–28 kcal/mole et de 57 kcal/mole.La barrière d'inversion du carbanion calculée pour l'anion vinyle est de 39 kcal/mole et l'isomérisation des imines se fait donc par inversion de l'azote. Les anions vinyliques ont une configuration stable.L'origine physique de ces barrières d'inversion est étudiée et caractérisée par les variations des termes énergétiques, de la composition de l'OM du doublet libre et des populations électroniques.La comparaison des processus d'inversion du carbanion, de l'azote et de l'oxonium dans la série CH2=CH, CH2=NH et CH2=OH a permis de mettre en évidence l'évolution des termes énergétiques, de la hauteur de la barrière et des transferts de population.
Theoretical conformational analysisIV. An ab initio SCF-LCAO-MO study of methylenimine and of vinyl anion
An ab initio SCF-LCAO-MO study of methylenimine and vinyl anion has been performed. The calculated barriers to nitrogen inversion and to rotation about the C=N bond are equal to 26–28 kcal/mole and 57 kcal/mole respectively.The calculated barrier to carbanion inversion in the vinyl anion amounts to 39 kcal/mole. Thus isomerization of imines occurs by a nitrogen inversion process and vinyl anions are configurationally stable.The physical origin of these inversion barriers is studied and characterized by the changes in the energy terms, in lone pair MO composition, and in electron populations.Comparison of the carbanion, nitrogen and oxonium inversion processes in the isoelectronic series CH2=CH, CH2=NH and CH2=OH permits to delineate general trends in the energy terms, barrier height and population transfers.

Zusammenfassung Für Methylenimin und das Vinylanion wird eine ab initio SCF-LCAO-MO-Studie durchgeführt. Die berechneten Barrieren für die Stíckstoffinversion und die Rotation um die C=N-Bindung betragen 26–28 kcal/Mol bzw. 57 kcal/Mol.Die berechnete Barriere für die Inversion des Carbanions im Vinylanion beträgt 39 kcal/Mol. Daher wird die Isomerisation von Iminen durch einen Stickstoffinversionsprozeß hervorgerufen, und die Konfigurationen von Vinyl-Anionen sind stabil.Der physikalische Ursprung dieser Inversionsbarrieren wird studiert und durch Änderungen in den Energietermen, in der Zusammensetzung von Ione pair-MO's und in den Besetzungszahlen der Elektronen charakterisiert.Ein Vergleich der Inversionsprozesse des Carbanions, des Stickstoffs und des Oxonium-Ions in der isoelektronischen Reihe CH2=CH, CH2=NH and CH2=OH+ ermöglicht es, allgemeine Züge in den Energietermen, in den Höhen der Barrieren und den Besetzungsübergängen abzuleiten.


Précédent article de cette série: cf. Réf. [1].

Laboratoire associé au C.N.R.S.  相似文献   
2.
This research work was proposed to study the antimicrobial activity of the silver nanocoated fabric with the purpose of producing good dressing and clothing material. We synthesized simple, ecofriendly, cost‐effective and sustainable silver nanoparticles by using the aqueous extract of Allium cepa L. Here, A. cepa L. acts as a good reducing and capping agent that produced stable silver nanoparticles having particle size of range 36 ± 1 to 98 ± 2 nm, Poly dispersiblity index 0.234 ± 0.61 to 1.023 ± 0.33 and Zeta potential ‐12 ± 1.5 mV to ‐26 ± 1.2 mV. The effect of temperature and extract volume used was considered for optimization of synthetic procedure. The nanocoated fabric was characterized for morphological study, size (using transmission electron microscopy (TEM) and field emission scanning electron microscopy (FE‐SEM) and zeta‐potential (Zeta Potentiometer). The presence of functional groups were observed by using attenuated total reflection‐Fourier transform infrared (ATR‐FTIR) and Raman spectroscopy. The crystallinity and structural property of the synthesized silver nanoparticles were studied in terms of Powder X‐ray diffraction (PXRD). An IC50 value and zone of inhibition was studied which demonstrate that the silver nanocoated fabric have an excellent antibacterial property against Gram‐negative (Escherichia coli) and Gram‐positive (Staphylococcus aureus) bacteria. Further nanocoated fabric material was washed (with function of time 0, 10, 25, and 50 laundry cycles) and still retained their anti‐bacterial activity towards both strain. Initially there was 52 μg/ml of silver nanoparticles on the cotton fabric but after 50 laundry cycle in 500 ml of distilled water the fabric showed 92% efficiency against gram positive and 90% efficacy toward gram negative bacteria. It was found that 4.16 μg/ml nano particles leached in case of S. Aureus and 5.2 μg/mL silver nanoparticles leached in case of E. coli. Nanocoated fabric material synthesized using green synthesis was found to be economical with good resistance to washing.  相似文献   
3.
Image segmentation is required to be studied in detail some particular features (areas of interest) of a digital image. It forms an important and exigent part of image processing and requires an exhaustive and robust search technique for its implementation. In the present work we have studied the working of MRLDE, a newly proposed variant of differential evolution combined with Otsu method, a well known image segmentation method for bi-level thresholding. The proposed variant, termed as Otsu+MRLDE, is tested on a set of 10 images and the results are compared with Otsu method and some other well known metaheuristics.  相似文献   
4.
We present a spherically symmetric solution of the general relativistic field equations in isotropic coordinates for perfect charged fluid, compatible with a super dense star modeling. The solution is well behaved for all the values of Schwarzschild parameter u lying in the range 0 < u < 0.1727 for the maximum value of charge parameter K = 0.08163. The maximum mass of the fluid distribution is calculated by using stellar surface density as ρ b = 4.6888×1014g cm?3. Corresponding to K = 0.08 and u max = 0.1732, the resulting well behaved solution has a maximum mass M = 0.9324M and radius R = 8.00 and by assuming ρ b = 2×1014g cm?3 the solution results a stellar configuration with maximum mass M = 1.43M and radius R b = 12.25 km. The maximum mass is found increasing with increasing K up to 0.08. The well behaved class of relativistic stellar models obtained in this work might has astrophysical significance in the study of internal structure of compact star such as neutron star or self-bound strange quark star like Her X-1.  相似文献   
5.
The aim of the present paper is to generalize the notion of reciprocal continuity and obtain common fixed point theorems in diverse settings as an application of the new notion. The new notion unifies the approaches of three well known notions- reciprocal continuity, subsequential continuity and conditional commutativity. Our results generalize and extend several fixed point theorems. We also demonstrate that the new notion is a necessary condition for the existence of common fixed points.  相似文献   
6.
In this paper, the electrical conductivity and relaxation studies in two different temperature regions (T?<?T m and T?>?T m) on plasticized PEO–PMMA blend polymer electrolyte system with AgNO3 salt are reported. The polymer electrolyte system has been prepared by solution cast technique and characterized by X-ray diffraction and differential scanning calorimetry. The conduction and relaxation processes at various temperatures have been investigated in the framework of modulus formalism. The distribution of relaxation times is discussed using Argand plot. Variation in ionic conductivity of polymer blends is discussed with the increase of PEO as well as with temperature.  相似文献   
7.
8.
Abstract

Two flavindogenides, 3-(2-chlorobenzylidene)-flavanone and 3-(2,4-dichloro- benzylidene)-flavanone reacted with six 5-substituted-2-aminobenzenethiols, the substituents being fluoro, chloro, bromo, methyl, methoxyl, and ethoxyl, to give respective 12 new compounds, 10-substituted-7-(2-chlorophenyl/2,4-dichlorophenyl)- 6H-6a,7-dihydro-6-phenyl[1]benzopyrano[3,4?c][1,5]benzothiazepines (5a–l) in 60–70% yields. The products were characterized on the basis of microanalytical data for elements and IR, 1 H, and 13 C NMR and mass spectral studies. All the synthesized compounds were evaluated for their antimicrobial activity against the bacteria,Escherichia coli and GFC,and the fungi,Aspergillus niger, Aspergillus flavus,and Curvularia lunata.  相似文献   
9.

Zinc salicylaldimine complex immobilized on silica gel was used as a promising catalyst for the transesterification reaction of dimethyl terephthalate (DMT) and ethylene glycol (EG).The catalyst was characterized by Fourier transform infra‐red spectroscopy (FT‐IR), thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The product bis‐(2‐hydroxyethyl)terephthalate (BHET)was confirmed by mass and 1H‐NMR studies. In comparison to zinc acetate i.e., homogeneous catalyst, a polymer supported catalyst showed better stability, catalytic activity and ease of separation from the reaction product. The catalyst can be reutilized during successive catalytic cycles.  相似文献   
10.
A radiotracer investigation was carried out in a diesel hydrotreater (DHDT) unit in a refinery for leak detection in a breech-lock heat exchanger system. The main objectives of the study were to identify the leaking heat exchanger in a system with six heat exchangers and estimate the leak rate. Bromine-82 as dibromobiphenyl was selected and used as radiotracer for the investigation. The radiotracer was instantaneously injected into the suction end of the feed pump line to the heat exchanger of the DHDT unit. The movement of the tracer was measured at strategically selected locations using NaI(Tl) scintillation detectors. Based upon the results of the radiotracer investigation, it was found that out of six heat exchangers, exchanger E-1F was leaking.  相似文献   
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