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111.
Soncini A Domene C Engelberts JJ Fowler PW Rassat A van Lenthe JH Havenith RW Jenneskens LW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(4):1257-1266
Why are some (4n+2)π systems aromatic, and some not? The ipsocentric approach to the calculation of the current density induced in a molecule by an external magnetic field predicts a four‐electron diatropic (aromatic) ring current for (4n+2)π carbocycles and a two‐electron paratropic (antiaromatic) current for (4n)π carbocycles. With the inclusion of an electronegativity parameter, an ipsocentric frontier‐orbital model also predicts the transition from delocalised currents in carbocycles to nitrogen‐localised currents in alternating azabora‐heterocycles, which rationalises the differences in (magnetic) aromaticity between these isoelectronic π‐conjugated systems. Ab initio valence‐bond calculations confirm the localisation predicted by the naïve model, and coupled‐Hartree–Fock calculations give current‐density maps that exhibit the predicted delocalised‐to‐localised/carbocycle–heterocycle transition. 相似文献
112.
《Surface and interface analysis : SIA》2005,37(9):737-742
A novel method that allows the determination of the electrical potential of a polymer surface has been applied for polypropylene film treated by N2 + H2 cold plasma. The plasma treatment results in formation on the film surface of NH2 groups, which then gets transformed to NH3+ in contact with an electrolyte and leads to the formation of an electrical double layer. The method consists of theoretical calculation of electrical model potential, using the measurement of the electrical capacitance of the film in contact with an electrolyte by dielectric spectroscopy. Comparison with the results obtained by theoretical model shows similar dependencies of the electrical potential as a function of amino‐groups density and electrolyte concentration, but systematic differences of absolute values are observed. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
113.
Sumio Kato Masataka Ogasawara Mikio Sugai Shinichi Nakata 《Catalysis Surveys from Asia》2004,8(1):27-34
Studies on the role of oxygen vacancy in structural change of nonstoichiometric perovskites and a property of oxygen-deficient perovskite-related K2NiF4 compounds are reviewed.The structural changes on which the authors focused are cation ordering and lattice distortion. The relationship between the distortion and oxygen vacancy was investigated by comparing the structures of Sr2(Sr1-xMx)TaO6-d (M = Ca2+ and Nd3+) solid solutions. It was found that distortion of a perovskite-type lattice decreased with an increasing amount of oxygen vacancies. In order to investigate the relationship between the cation ordering on octahedral sites and oxygen vacancy, structures of stoichiometric Sr2-xLaxCo1-yTa1+yO6 and oxygen-deficient Sr2-xLaxMg1-yTa1+yO6-d solid solutions were compared. The authors' work reveals that the cation ordering affects the amount of oxygen vacancies in addition to cation charge and size. 相似文献
114.
Clean-up and analysis of carbazole and acridine type polycyclic aromatic nitrogen heterocyclics in complex sample matrices 总被引:1,自引:0,他引:1
A HPLC method for the analysis of polycyclic aromatic nitrogen heterocyclics (PANHs) in complex sample matrices is presented. It isolated and separated carbazole and acridine type PANHs with an absolute recovery of between 79–98%. Open column chromatography is used as an initial step to isolate a PANH fraction. By applying normal-phase liquid chromatography using a dimethylaminopropyl silica stationary phase and utilising back-flush technique it was possible to separate the PANH fraction into two fractions containing acridine type and carbazole type PANHs, respectively. The method applied on a sample of solvent refined coal heavy distillate (SRC II HD). A number of 3–5 ring acridines and carbazoles were identified with GC–electron impact MS and quantified with GC–nitrogen–phosphorous detection. Polycyclic aromatic hydrocarbons (PAHs) were determined in the SRC II HD sample by automated on-line clean-up and analysis of the obtained PAH fraction with coupled LC–GC–flame ionization detection. There was no overlap between the PANH and the PAH fractions with this method, and carbazoles and acridines were efficiently separated. 相似文献
115.
3-[1′(1′H)-Substituent-pyrazol-5′-yl]benzo[5,6]coumarins and 3-(1′,2′-oxazol-5′-yl)benzo[5,6]coumarin were prepared via condensation of 3-(2′-formyl-1′-chlorovinyl)benzo[5,6] coumarin with hydrazine derivatives or hydroxylamine.Reaction of 3-[1′(1′H)-pyrazol-5′-yl]benzo[5,6]coumarin with alkyl halides,olefinic compunds or acid chlorides are described. 相似文献
116.
Specific sorption sites for nitrogen, N2, in NaLSX and LiLSX zeolites were investigated using a DRIFT spectroscopic method. Sorption of molecular hydrogen, H2, by NaLSX or LiLSX zeolite at 77 K with DRIFT control of perturbation of sorbed molecules allowed to discriminate two or three different types of specific sorption sites in the respective zeolites. Their H–H stretching frequencies are 4077 and 4081 cm–1 for NaLSX, and 4061, 4084 and 4129 cm–1 for LiLSX. With reference to an independent investigation by methods of both sorption thermodynamics and molecular modeling for N2 sorption on LiLSX, the first two of the corresponding bands were ascribed to H2 sorption on lithium cations, Li+, localized in supercages of the faujasite, FAU, zeolite framework at sites SIII and SIII, while the latter band most likely belongs to H2 sorption on Li+ cations at sites SII, and on hydroxyl groups, OH. Sorption of N2 by Li+ cations at sites SIII and SIII is the strongest, resulting in a decrease of intensity of the corresponding DRIFT bands that stem from subsequent H2 sorption. Nitrogen sorption by Li+ cations at sites SII is much weaker. Sorption of N2 on Na+ cations at sites SIII in NaLSX zeolite is also stronger than by Na+ cations at sites SII. 相似文献
117.
金属/氮/碳催化剂(M/N/C,M=Fe、Co等)是最有发展前景的非贵金属电催化剂之一,其性能依赖于催化剂表面的活性物种密度.通过常规的热解含氮前驱物与金属盐的方法制得的催化剂往往存在金属活性物种被包埋而不能有效利用的缺点.考虑到石墨相氮化碳(g-C3N4)富含类吡啶氮和亚纳米孔腔结构,将g-C3N4包覆在高导电性碳纳米笼(hCNC)表面,进而利用表层g-C3N4的配位和限域作用锚定大量Co2+离子,获得的Co/g-C3N4/hCNC复合物经热解后形成了活性位高度暴露、导电性好、孔结构丰富的Co/N/C催化剂.800℃热解得到的最优化催化剂在碱性介质中展现出优异氧还原活性,其起始电位(0.97 V)与商业Pt/C催化剂相当,且抗甲醇干扰性能和稳定性优异.此项研究提供了一种构建具有高度暴露活性位的M/N/C催化剂的有效策略. 相似文献
118.
Ab initio molecular orbital theory and density functional theory have been employed to study N14 cluster with low spin at the HF/6-31G*, B3LYP/6-31G*, B3PW91/6-31G*, BP86/6-31G*, and BHLYP/6-31G* levels of theory. Twelve isomers were studied, including one previously investigated cage molecule. The most stable isomer of N14 is a C
2h
-symmetric molecule that contains two separated five-membered nitrogen rings connected by a —N=N—N=N— bridge. The second, third, and fifth most stable isomers each have one five-membered nitrogen ring. The theoretical results suggest that the five-membered nitrogen ring gives rise to a particularly stable structural unit, and the more side chains that the five-membered nitrogen ring links with, the less stable the structure will become. 相似文献
119.
120.